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NITROCOMPUESTOS

Estos compuestos se nombran considerando al grupo -NO2

como un sustituyente

nitro

nitrometano

nitrobenceno

Nitro Compuestos alifaacuteticos

Nitro Compuestos aromaacuteticos

Nomenclatura de los Nitro Compuestos

El aacutetomo de nitroacutegeno es trigonal

plano con aacutengulos de enlace de 120deg Hay dos formas resonantes que implican que los dos aacutetomos de oxiacutegeno son equivalentes

Estructura

Efectos electroacutenicos

Los grupos nitro son grupos electroatractores tanto por efecto inductivo ‐I como por efecto resonante ‐ R Esto significa que tanto el enlace C‐N y el sistema π estaacuten fuertemente polarizados

EFECTO -R

El grupo ‐NO2

en el nitrobenceno hace sentir su efecto por

resonancia ndashR

en las posiciones orto y para a traveacutes de los

enlaces π Tambieacuten opera el efecto ndashI pero este es menos

obvio

EFECTO -I

Debido al efecto inductivo -I en el enlace σ los valores de pKa

de los compuestos conteniendo al

grupo nitro se ven afectados

Propiedades fiacutesicasAl comparar a los nitrocompuestos con otros compuestos aromaacuteticos que tengan el mismo peso molecular se observa eg un incremento en el punto de ebullicioacuten fuera de proporcioacuten

Propiedades fiacutesicasO

NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)

Los nitrocompuestos son insolubles en agua a menos que contengan dentro de su estructura un grupo que interacciones con ella

Siacutentesis de Nitro-Compuestos

Los nitro compuestos alifaacuteticos se sintetizan por

Nitracioacuten en fase gaseosa de alcanosReaccioacuten SN2 de nitrito sobre halogenuros de alquiloNitracioacuten electrofiacutelica

de aniones enolato

Oxidacioacuten de aminas con peraacutecidos

Nitracioacuten en fase gaseosa de alcanos


Este es un proceso industrial que ocurre a traveacutes de radicales libres y que involucra al radical NO2



CH3CH2CH2CH3 + HNO3420 Co

NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45


CH3CH2CH2CH2CH3 + HNO3420 Co

CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +

CH3 CH2HC CH2 CH3NO2

202

Cuando se hace reaccionar al nitrito de sodio (el cual actuacutea como un nucleoacutefilo

ambivalente a traveacutes del O o

del N como nucleoacutefilos) se obtienen dos productos un nitro compuesto o bien un eacutester nitrito

Reaccioacuten SN2 de nitrito sobre halogenuros de alquilo



I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30


El uso de nitrito de plata produce uacutenicamente el nitro compuesto

El AgNO2 es insoluble en eacuteter por lo que se evitan reacciones laterales



AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co

NO HAY REACCIOacuteN



NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO




El uso de los aniones enolato

de compuestos con metilenos activos forman un producto muy estable debido a la formacioacuten de un quelato

con el contraion

Nitracioacuten electrofiacutelica

de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80



Los nitro compuestos se pueden obtener por medio de la oxidacioacuten de aminas con peraacutecidos



NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2


Oxidacioacuten de oximas

con peraacutecidos


Nitro compuestos aromaacuteticos

Estos son sintetizados por medio de la reaccioacuten de sustitucioacuten electrofiacutelica

aromaacutetica (SEA) con iones NO2

+

como electroacutefilos


MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)

MEZCLA USADA PARA LLEVAR A CABO LA NITRACIOacuteN SOBRE ANILLOS DISUSTITUIacuteDOS O TRISUSTITUIacuteDOS

(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmLCl Cl Cl

NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3

(CONCENTRADO) + AcOH(65 A 70 )

d = 14 A 142 gmL

MEZCLAS NITRANTES

Condiciones maacutes suaves

El El grupogrupo controlacontrolala la regioquregioquiacuteiacutemicamica

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS

REACIONES DE NITROCOMPUESTOS

AacuteCIDO-BASEFormacioacuten de Aniones Las bases conjugadas se forman con facilidad cuando se tratan con una base fuerte Dichos aniones se encuentran estabilizados por resonancia (aniones nitronato)

ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+

Los protones en el nitrometano MeNO2

tienen un pKa de 102 por lo que una base apropiada para llevar a

cabo la reaccioacuten aacutecido-base podriacutea ser el KOH Como el ion

nitronato

esta deslocalizado es una base blanda

que reacciona con aacutecidos blandos



Reaccioacuten de Henry Esta es una reaccioacuten anaacuteloga a la reaccioacuten Aldoacutelica

Henry L Compt Rend 1895 120 1265

ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH

MECANISMO REACCIOacuteN DE HENRY

ELIMINACIOacuteN E1

BC

Si el aldehiacutedo es alifaacutetico se necesita utilizar anhiacutedrido aceacutetico para llevar a cabo la eliminacioacuten

ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE

REACCIOacuteN DE HENRY

(+)-N-metilefedrina DIPEA = (iso-Pr)2

EtN

A New

Copper

Acetate-Bis(oxazoline)-Catalyzed Enantioselective

Henry Reaction

D A Evans D Seidel M Rueping H W Lam J T Shaw C W Downey J Am Chem Soc 2003 125 12692-12693

Cloruro de cetiltrimetilamonio

(CTACl)

Nitroaldol

Reaction in Aqueous Media An Important Improvement of the Henry Reaction

R Ballini G Bosica J Org Chem 1997 62 425-427

A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions

J M Concelloacuten P L Bernad H Rodriacuteguez-Solla C Concelloacuten J Org Chem 2007 72 5421-5423

SmI2

= yoduro de Samario

Ephedrine (EPH) is a sympathomimetic

amine

commonly used as a stimulant appetite suppressant concentration aid decongestant and to treat hypotension

associated with anaesthesia Ephedrine is similar in structure to the synthetic derivatives amphetamine

and methamphetamine Chemically it is an alkaloid

derived from various plants in the genus Ephedra (family Ephedraceae) It is most usually marketed in the hydrochloride and sulfate forms

Los aniones nitronato

por si mismos pueden actuar como nucleoacutefilos

ambidientes

que pueden actuar

tanto por el C (nucleoacutefilo

suave) o por el O (nucleoacutefilo fuerte) Estos centros reaccionaraacuten con electrofilos

(suaves o duros respectivamente)

NUCLEOacuteFILOS AMBIDIENTES

La adicioacuten de Michael es una adicioacuten conjugada al doble enlace de un centro aacutecido suave de un eacutester siendo el grupo carbonilo el centro aacutecido duro

Adicioacuten de Michael

Arthur Michael nacioacute

en Buffalo New

York

REACCIOacuteN DE MICHAEL

Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic

Liquid [bmIm]OH in Michael Addition

of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles

B C Ranu S Banerjee Org Lett 2005 7 3049-

3052

John Ulric Nef1862-1915

John Ulric Nef (Johann Ulrich Nef) nacio

en suiza y sus padres emigraron a norteamerica Descubriacuteo

la reaccioacuten de Nef

REACCIOacuteN DE NEF


NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85

1) NaOH H2O2) H2SO4 H2O 5 Co

OCH3O

O

65

REACCIOacuteN DE NEFREACCIOacuteN DE MICHAEL

Este comportamiento ambivalente se puede ver en la reaccioacuten Nef


Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic

Nitroalkenes Catalytic

Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones

C A Luchaco-Cullis A H Hoveyda J Am Chem Soc 2002 124 8192-8193


Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Simple Conversion of Nitro Group Into Carbonyl GroupSynthetic Communications 1998 28(16) 3057-3064

Paolo Ceccherellidagger

Massimo Curini Maria Carla Marcotullio Francesco Epifano

and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75


Sustrato Producto Rendimiento ()

Nitrociclohexano

(15) Ciclohexanona (9) 81

5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona

(37)Mono-etilidencetal

de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima

5-acetoxi-2-nitrohexano

(5) 5-acetoxi-2-hexanona

(14) 93

5-Nitro-2-hexanol

TBDMS eacuteter (6) 5-hidroxi-2-hexanona

TBDMS eacuteter (15) 88

3-(1-Nitroetil)-ciclohexanol (79) 3-Acetilciclohexanol

(16) 85

1-Nitrohexano

(85) Aacutecido hexanoiacuteco

(17a) 98

4-Nitro-2-butanol (910) Aacutecido 3-Hidroxibutiacuterico

(1812) 70

Fenilnitrometano

(1011) Aacutecido benzoiacuteco

(19a) 91

a Los productos de la reaccioacuten se caracterizaron por comparacioacuten con una muestra auteacutentica (espectros de IR RMN-1H y por datos de GC-MS)

b Rendimiento del producto aislado

REACCIOacuteN CON OXONO


OHO

o o

ORBITAL HOMO DE MAacuteS ALTA ENERGIacuteAORBITAL LUMO DE LA MOLEacuteCULA ACEPTORA

EFECTO α

DEL HETEROAacuteTOMO

MECANISMO DE LA OXIDACIOacuteN DE UN ALDEHIacuteDO CON OXONO


O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX

Unprecedented selective Nef reaction of secondary nitroalkanes promoted by DBU under basic homogeneous conditionsR Ballini G Bosica D Fiorini M Petrini Tetrahedron Lett 2002 43 5233-5235

REACCIOacuteN DE NEFA New Method for the Conversion of Nitro Groups into CarbonylsJOHN E McMURRY

AND JACK MELTON J Org Chem 1973

Vol 38

[66]

4367-4373

El meacutetodo reductivo permite obtener oximas las cuales pueden hidrolizadas a los compuestos carboniacutelicos

correspondientes El titanio (III) permite reducir el enlace N-O ya que el titanio muestra una fuerte afinidad hacia el oxiacutegeno lo cual facilita la hidroacutelisis completa para que ocurra la conversioacuten


REACCIOacuteN CON TICl3 RUPTURA EDUCTIVA

NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H

REACCIOacuteN REDOX FORMACIOacuteN DE LA OXIMA

NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+

REACCIOacuteN DE HIDROacuteLISIS DE LA OXIMA

Et2 OmiddotBF3 + 2 Et2 O + 3 C2 H3 (O)CH2 Cl rarr 3 Et3 O+BF4- + B[(OCH(CH2 Cl)CH2 OEt]3

Hans Meerwein (Mayo 20 1879 Hamburgo Alemania

ndash

Octubre

24 1965 Marburgo Alemania)

Hans Meerwein

alrededor de sus estudiantes debajo de los doctores Graeb Bieker Muumlller Haffner Gies von

Rinteln

y otros La fotografiacutea proviene de la herencia del famoso quiacutemico

O-ALQUILACIOacuteN DE UN ANIOacuteN NITRONATO CON EL REACTIVO DE MEERWEIN

La O-alquilacioacuten es posible con un agente alquilante duro

como el reactivo de Meerwein

que actuacutea como

una fuente de Me+

La naturaleza ambidiente

del grupo nitro hace que eacuteste sea un reactivo muy versaacutetil

ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN

En principio la reduccioacuten de un grupo nitro debe de seguir los siguientes paso

La reduccioacuten de los grupos nitroso en general es maacutes faacutecil de llevar a cabo pero la ventaja de la reduccioacuten de los grupos nitro es que esta se puede llevar a cabo de diferentes maneras

Panorama General

Se pueden usar metales como Fe Zn Sn los cuales en presencia de medio H+ permiten reducir el grupo ndashNO2 por una secuencia de dos reacciones transferencia de un solo electroacuten (Single Electron Transfer (SET))protonacioacuten

REDUCCIOacuteNREACCIOacuteN METAL H+

ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )

El mecanismo para la reaccioacuten ZnH+

es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o

REDUCCIOacuteNMEDIO BAacuteSICO



ON

OZn

NaOH

EtOHCALOR

N N

AZOBENCENO(84 A 86 )



MECANISMO transferencia de un solo electroacuten (Single Electron Transfer (SET)


MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN

Las reacciones de H2

Pd

(o bien Pt) se puede utilizar para llevar a cabo una reaccioacuten en la que se transfiere heterogeneamente

un H-

a la superficie del metal y de eacuteste al grupo nitro

HIDROGENACIOacuteN CATALIacuteTICA

H2

Pd

soportado en carbono

Palladium-catalyzed

reduction

of

aromatic

nitro groups

to

amines can be accomplished

in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and

polymethylhydrosiloxane

(PMHS) for

aromatic

nitro groups Aliphatic

nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF

R J Rahaim R E Maleczka

(Jr) Org Lett 2005 7 5087-5090

A microwave-assisted palladium-catalyzed

catalytic

transfer hydrogenation

of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields

by simple liquid-liquid

extraction

El bisulfuro de sodio (NaSH) o el polisulfuro

de sodio (Na2

Sx

) o el sulfuro de amonio ((NH4

)2

S2

) se pueden utilizar para reducir regioselectivamente

un grupo nitro

de otros presentes en la misma moleacutecula y es posible que dicha reaccioacuten tambieacuten proceda a traveacutes de reacciones SET

REACTIVOS CON AZUFRE (S)


NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)

Zinin N Ann Chem Pharm

1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]

NITRO NITROSO ALQUIL-HIDROXILAMINA AMINA

ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H

N-FENILHIDROXILAMINA

O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO

Los reactivos como el LiAIH4

(pero no el NaBH4

) pueden reducir al grupo nitro por la transferencia de un hidruro H- El producto dependeraacute

de la

naturaleza del agente reductor pero el punto final seraacute

una amina

HIDRUROS METAacuteLICOS

4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl

Otra manera de obtener LAH

Reaccioacuten de metatesis

LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema

descomposicioacuten del LAH en presencia de agua

Sin embargo

excelente agente reductor

epoacutexido

aldehiacutedo cetona

eacutester

Aacutecido carboxiacutelico

luego luegooacute

Reduction of Organic Compounds by Lithium Aluminum HydrideIII Halides Quinones Miscellaneous Nitrogen Compounds1Robert F Nystrom and

Weldon G BrownJ Am Chem Soc 1948 70 (11) 3738-3740 bull

DOI 101021ja01191a057

NITROCOMPUESTOS AROMAacuteTICOS

NITROCOMPUESTOS ALIFAacuteTICOS

24 3 2

2

2

2

(b)(i) LiAlH4 THF reflujo (ii) Boc2O NaHCO3 THFH2O

(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112

Trace Amine-Associated Receptor Agonists Synthesis and Evaluation of Thyronamines and Related Analogues

Matthew E Hart Katherine L Suchland Motonori

Miyakawa James R Bunzow David K Grandy and

Thomas S Scanlan

REACCIOacuteN DE SNA (MEISENHEIMER)

Jakob Meisenheimer(14 junio de 1876 ndash

2 diciembre de 1934)Quiacutemico alemaacuten



INFLUENCIA DEL TIPO DE NUCLEOacuteFILO

Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000


INFLUENCIA DELNUCLEOacuteFUGO


INFLUENCIA DELGRUPO

ELECTROATRACTOR

MIECZYSLAW MAKOSZA Y JERZY WINIARSKI EN 1987

Vicarious

nucleophilic

substitution

of

hydrogen Mieczysław

Mąkosza

and

Jerzy Winiarski Acc Chem Res 1987 20(8) pp

282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure

amp Appl Chem Vol 69 No 3 pp 559-564 1997

REACCIOacuteN DE SNA VICARIA



NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H

MECANISMO DE REACCIOacuteN

A R Katritzky L Xie Tetrahedron Lett 1996 37 347-350

para-Formylation of nitroarenes via vicarious nucleophilic substitution of hydrogen with tris(benzotriazol-1-yl)methane

Reaction

of

nitroarenes

with

tris(benzotriazol-1-yl)methyl

anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields

111-Trimethylhydrazinium

Iodide A Novel Highly

Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen

P F Pagoria A R Mitchell R D Schmidt J Org Chem 1996 61 2934-2935

TMHI that

is

easily

prepared

from

11-dimethylhydrazine is

a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents

Mecanismo de reaccioacuten propuesto

Hydroxylation of Nitroarenes with Alkyl Hydroperoxide Anions via Vicarious Nucleophilic Substitution of Hydrogen

M Makosza K Sienkiewicz J Org Chem 1998 63 4199-4208

Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted

o- and p-nitrophenols The

reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta

muy desprotegido (polarizado)

IR

RMN ndash 1H

Para un protPara un protoacuteoacuten CH adyacente a el grupo n CH adyacente a el grupo ndashndashNO2NO2 se observa un desplazamiento quse observa un desplazamiento quiacuteiacutemico mico δδ

= 43 = 43

debido al efecto debido al efecto electroatractorelectroatractor

UV

El grupo nitro da lugar a un desplazamiento El grupo nitro da lugar a un desplazamiento pronunciado de la pronunciado de la λλ

en la que se presenta la en la que se presenta la εε

maxmax

hacia longitudes de onda mhacia longitudes de onda maacuteaacutes largas cuando ests largas cuando estaacuteaacute

conjugado a sistemas insaturados conjugado a sistemas insaturados ππ el cual es un el cual es un efecto efecto batocrbatocroacuteoacutemicomico Esta es la causa por la que los Esta es la causa por la que los nitro compuestos con frecuencia son de color amarillonitro compuestos con frecuencia son de color amarillo

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RMN ndash 1H

UV

Estos compuestos se nombran considerando al grupo -NO2

como un sustituyente

nitro

nitrometano

nitrobenceno

Nitro Compuestos alifaacuteticos

Nitro Compuestos aromaacuteticos

Nomenclatura de los Nitro Compuestos



Estructura



EFECTO -R

El grupo ‐NO2


resonancia ndashR



obvio

EFECTO -I






NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



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RMN ndash 1H

UV



Estructura



EFECTO -R

El grupo ‐NO2


resonancia ndashR



obvio

EFECTO -I






NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 118

RMN ndash 1H

UV



EFECTO -R

El grupo ‐NO2


resonancia ndashR



obvio

EFECTO -I






NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

EFECTO -I






NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 114

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Slide Number 117

Slide Number 118

RMN ndash 1H

UV



NO

pe 210 Co

pf 57 Co

ON

O

ON

O

ON

O

ONO

ON O

ON

O

pe 319 Co

pf 118 Co

pe 303 Co

pf 898 Co

pe 299 Co

pf 174 Co

(774 mm Hg)

(770 mm Hg)

(777 mm Hg)





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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RMN ndash 1H

UV





de aniones enolato








NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV







NO2H3C CH3 CH2 NO2

10 13

+ CH3 CH2 CH2+ NO2

8 +

CH3 CH2 CH2 CH2 NO2

24

CH3 CH CH2 CH3NO2

45



CH3 CH2 CH2 CH2 CH2

189

CH3 CH CH2 CH2NO2

182

NO2 CH3+ +


202







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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RMN ndash 1H

UV







I+ NaNO2

EtOH

H2O N+

OO O

N O

58 30






AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 118

RMN ndash 1H

UV





AgNO2

Et2ONO

O

80

Br +0 a 25 Co

AgNO2

Et2OCl +

0 a 25 Co

AgNO2

Et2ONO

O

82

I +0 a 25 Co




NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


NaNO2 NO

O

61 BrH+

NaNO2

DMFBr +

NaNO2 NO

O

60 +

N + O

O

O N O

60 20

O N O

20

+

I

DMF

DMSO






con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

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RMN ndash 1H

UV





con el contraion


de aniones enolato

CH2

OCH3O Na

CH2

O

H

CH3O H + NaCH2

O

NO

OOH3C

CH

O

H

NO

O + CH3O NaC

O

H

NO

O CH3O H+

Na

QUELATOMUY ESTABLE



de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 117

Slide Number 118

RMN ndash 1H

UV


de aniones enolato

NO

OO

NOO

CH2O K

CH3

CH3

75

K

CH2

O

OEt

NO

OO

CH2O K

CH3

CH3

CH2

NO

O

H

K+

O

OCH2CH3O

CH3CH2

80






NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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RMN ndash 1H

UV





NH H CF3

O

O

OH

(3 EQUIVALENTES)N

O O

NO2NO2



con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 118

RMN ndash 1H

UV


con peraacutecidos





+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




+



MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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RMN ndash 1H

UV

MEZCLAS NITRANTES

HNO3

(FUMANTE) +

H2

SO4

(FUMANTE)


(10 DE SO3

)(95 A 100 )

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 118

RMN ndash 1H

UV

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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RMN ndash 1H

UV

CH3NO2

NO2

HNO3 (f)

H2SO4 (f)

40 Co

CH3NO2

NO2

O2N

3 h 98

KMnO4

H2O

CNO2

NO2

O2N

O OH

H2SO4NO2

NO2

O2NH

70

(10 DE SO3

)(95 A 100 )

HNO3

(FUMANTE) + H2

SO4

(FUMANTE)

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 3

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Slide Number 118

RMN ndash 1H

UV

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)


NO2

NO2

+HNO3 (c)

H2SO4 (c)

40 Co

HNO3 (c)H2SO4 (c)

90 Co

Cl

NO2

NO2

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 7

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(98 )(65 A 70 )HNO3

(CONCENTRADO) + H2

SO4

(CONCENTRADO)

d = 14 A 142 gmL d = 184 gmL

MEZCLAS NITRANTES

C

39

C

47

53

C

31

69

C

18

82

HH

CH3HH

CH3H3CH

CH3H3CCH3

H

61

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

MEZCLAS NITRANTES

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(98 )KNO3

+ H2

SO4

(CONCENTRADO)

d = 184 gmL

2

3

2 4

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

(95 A 100 )

HNO3

(FUMANTE) + Ac2

O

MEZCLAS NITRANTES

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES



HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 118

RMN ndash 1H

UV


HNO3


d = 14 A 142 gmL

MEZCLAS NITRANTES

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

PROBLEMAS

MEZCLAS NITRANTES

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

PROBLEMAS



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



ON

OH

Base

ON

OH

Base H

ON

O+

ANIONNITRONATO

+




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




nitronato







ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

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Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




ON

O

H

O

ONOO

H

HO

NOO

H

H

ONOH


ELIMINACIOacuteN E1

BC


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


ON

OR H

O

+ ON

H

O

R

OHO

O O

N

ONO

R

H


EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

EJEMPLO RECIENTE



EtN

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

A New

Copper


Henry Reaction



(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


(CTACl)

Nitroaldol



A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

A Convenient

Samarium-Promoted

Synthesis

of

Aliphatic

(E)-Nitroalkenes

under

Mild

Conditions


SmI2

= yoduro de Samario


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


amine







ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



ambidientes

que pueden actuar








en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




en Buffalo New

York


Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

Ionic

Liquid

as Catalyst

and

Reaction

Medium The

Dramatic

Influence

of

a Task-Specific

Ionic


of

Active Methylene

Compounds

to

Conjugated

Ketones Carboxylic

Esters and

Nitriles


3052







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV







NO2OCH3

O

CH3

NCH3

CH3

HO

OCH3NO2

O

85


OCH3O

O

65




Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones



Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

Cu-Catalyzed

Enantioselective

Conjugate

Addition

of

Alkylzincs

to

Cyclic


Asymmetric

Synthesis

of

Cyclic

α-Substituted

Ketones






and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




and

Ornelio

Rosati

O

NO2 KSO5H

CH3OHNa2HPO4

NaOH (1N)

25 C 1ho

O

O

75



Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

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Slide Number 35

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


Nitrociclohexano


5-Nitro-2-hexanona

(26) 25-hexanodiona

(12a) 75Etilencetal

de la 5-Nitro-2-

hexanona


de la 25-

hexanodiona

(137) 87

5-Nitro-2-hexanol

(48) Materia prima



(14) 93

5-Nitro-2-hexanol




(16) 85

1-Nitrohexano


(17a) 98


(1812) 70

Fenilnitrometano


(19a) 91





OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



OHO

o o


EFECTO α




O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 49

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Slide Number 51

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Slide Number 85

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Slide Number 88

Slide Number 89

Slide Number 90

Slide Number 91

Slide Number 92

Slide Number 93

Slide Number 94

Slide Number 95

Slide Number 96

Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



O

H

O O SO

OO K

O

H

HOH

O

H

O O SO

OO K

H

O H

O

OHO H

H+

HO O S

O

OO K

H

O H

O H

O

O K

REACCIOacuteN REDOX




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




Vol 38

[66]

4367-4373





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 40

Slide Number 41

Slide Number 42

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Slide Number 51

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Slide Number 53

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Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV





NO

O

H

NO

O

H TiCl

ClCl N

O

O

H

TiCl

Cl

(III)

TiCl3 + Cl

NO

O

H

TiCl

Cl

(III)

TiCl4+TiCl3NO

O

H

TiCl

Cl

(III)

TiCl3

NO

O

H

TiCl

Cl+

(III)

H O H

NO

H

H+ TiCl3HO

(IV)

HO H


NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

NO

H

H

H O H+ NO

H

H

OH

H H O H

H O HH

NO

H

H

O HHN

O

H

HO H H

+

NO

H

H

OHH

+




ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



ndash

Octubre


Hans Meerwein


Rinteln





que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



que actuacutea como

una fuente de Me+



ONC

O

H

R

H3C OCH3

CH3

BF4

H3C O S

O

OF

oacute

NCO

H

R

O CH3

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

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Slide Number 101

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Slide Number 103

Slide Number 104

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Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

REDUCCIOacuteN



Panorama General



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 13

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



ON

O

NITRO

Zn HClNH2

ON

O

NITRO

NNH4Cl

ZnOH

H

ON

O

NITRO

NTHF

BH3OH

H

(70 )

(80 )

(80 )


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

Slide Number 12

Slide Number 13

Slide Number 14

Slide Number 15

Slide Number 16

Slide Number 17

Slide Number 18

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Slide Number 20

Slide Number 21

Slide Number 22

Slide Number 23

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Slide Number 29

Slide Number 30

Slide Number 31

Slide Number 32

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Slide Number 38

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Slide Number 40

Slide Number 41

Slide Number 42

Slide Number 43

Slide Number 44

Slide Number 45

Slide Number 46

Slide Number 47

Slide Number 48

Slide Number 49

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Slide Number 51

Slide Number 52

Slide Number 53

Slide Number 54

Slide Number 55

Slide Number 56

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Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

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Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


es

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

NITROSOR N O

H ClR N O H

Cl

Zno

R N O H

Zn Cl(I)

R N O HZn Cl(II)

H Cl

+ Zn Cl(II)

ClR N O H

HHIDROXILAMINA

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 110

Slide Number 111

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

o




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




ON

OZn

NaOH

EtOHCALOR

N N






MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




MEDIO BAacuteSICO

NR O NROH

H+

NaOHR N N R

O

AZOXI

2 eR N N R

AZO

2 eR N N R

H HH2ONaOHH2O

NaOHH2O

HIDRAZO

Zn HClCALOR

Zn HClCALOR

Zn HClCALOR

R NH2 R NH2R NH2

REDUCCIOacuteN


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 13

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Slide Number 17

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Slide Number 104

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Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


Pd


un H-



H2

Pd


Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 40

Slide Number 41

Slide Number 42

Slide Number 43

Slide Number 44

Slide Number 45

Slide Number 46

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Slide Number 48

Slide Number 49

Slide Number 50

Slide Number 51

Slide Number 52

Slide Number 53

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Slide Number 100

Slide Number 101

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Slide Number 103

Slide Number 104

Slide Number 105

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Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

Palladium-catalyzed

reduction

of

aromatic

nitro groups

to


in high

yield with

wide

functional

group

tolerance

and

short reaction

times at rt using

aqueous

potassium

fluoride

and


(PMHS) for

aromatic


nitro compounds

are reduced

to

the

corresponding

hydroxylamines

using

triethylsilane

instead

of

PMHSKF


(Jr) Org Lett 2005 7 5087-5090


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

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Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


catalytic


of

different

homo-

or

heteronuclear

organic

compounds

using

formate

salts

as a hydrogen

source

was

performed

in ([bmim][PF6

] Essentially

pure

products

could

be isolated

in moderate

to

excellent

yields


extraction


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


de sodio (Na2

Sx


)2

S2


un grupo nitro




NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


NO2

NO2

1) S8 NaOH

55 CoNaOH

2) HCl

NH2

NO2

3) NaOH (80 )

N N Zinin (1812-1880)


1842 44 283-287 1844 52 361-362 1853 85328-329

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 77

Slide Number 78

Slide Number 79

Slide Number 80

Slide Number 81

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Slide Number 83

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Slide Number 85

Slide Number 86

Slide Number 87

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Slide Number 89

Slide Number 90

Slide Number 91

Slide Number 92

Slide Number 93

Slide Number 94

Slide Number 95

Slide Number 96

Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ON

O

+ SSS

S SS

SS

ONO

SSS

S SS

SS

ONO SS

SS S

S

SS

+H O H

ON

OH

NO

O H+

O H

SSS

S SS

SS

OH

SSS

S SS

SS

OH

O HSS

SS S

S

SS

O

+ H O H

NITROSOBENCENO

O H

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 21

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Slide Number 24

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Slide Number 90

Slide Number 91

Slide Number 92

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Slide Number 95

Slide Number 96

Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

Slide Number 12

Slide Number 13

Slide Number 14

Slide Number 15

Slide Number 16

Slide Number 17

Slide Number 18

Slide Number 19

Slide Number 20

Slide Number 21

Slide Number 22

Slide Number 23

Slide Number 24

Slide Number 25

Slide Number 26

Slide Number 27

Slide Number 28

Slide Number 29

Slide Number 30

Slide Number 31

Slide Number 32

Slide Number 33

Slide Number 34

Slide Number 35

Slide Number 36

Slide Number 37

Slide Number 38

Slide Number 39

Slide Number 40

Slide Number 41

Slide Number 42

Slide Number 43

Slide Number 44

Slide Number 45

Slide Number 46

Slide Number 47

Slide Number 48

Slide Number 49

Slide Number 50

Slide Number 51

Slide Number 52

Slide Number 53

Slide Number 54

Slide Number 55

Slide Number 56

Slide Number 57

Slide Number 58

Slide Number 59

Slide Number 60

Slide Number 61

Slide Number 62

Slide Number 63

Slide Number 64

Slide Number 65

Slide Number 66

Slide Number 67

Slide Number 68

Slide Number 69

Slide Number 70

Slide Number 71

Slide Number 72

Slide Number 73

Slide Number 74

Slide Number 75

Slide Number 76

Slide Number 77

Slide Number 78

Slide Number 79

Slide Number 80

Slide Number 81

Slide Number 82

Slide Number 83

Slide Number 84

Slide Number 85

Slide Number 86

Slide Number 87

Slide Number 88

Slide Number 89

Slide Number 90

Slide Number 91

Slide Number 92

Slide Number 93

Slide Number 94

Slide Number 95

Slide Number 96

Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

Slide Number 12

Slide Number 13

Slide Number 14

Slide Number 15

Slide Number 16

Slide Number 17

Slide Number 18

Slide Number 19

Slide Number 20

Slide Number 21

Slide Number 22

Slide Number 23

Slide Number 24

Slide Number 25

Slide Number 26

Slide Number 27

Slide Number 28

Slide Number 29

Slide Number 30

Slide Number 31

Slide Number 32

Slide Number 33

Slide Number 34

Slide Number 35

Slide Number 36

Slide Number 37

Slide Number 38

Slide Number 39

Slide Number 40

Slide Number 41

Slide Number 42

Slide Number 43

Slide Number 44

Slide Number 45

Slide Number 46

Slide Number 47

Slide Number 48

Slide Number 49

Slide Number 50

Slide Number 51

Slide Number 52

Slide Number 53

Slide Number 54

Slide Number 55

Slide Number 56

Slide Number 57

Slide Number 58

Slide Number 59

Slide Number 60

Slide Number 61

Slide Number 62

Slide Number 63

Slide Number 64

Slide Number 65

Slide Number 66

Slide Number 67

Slide Number 68

Slide Number 69

Slide Number 70

Slide Number 71

Slide Number 72

Slide Number 73

Slide Number 74

Slide Number 75

Slide Number 76

Slide Number 77

Slide Number 78

Slide Number 79

Slide Number 80

Slide Number 81

Slide Number 82

Slide Number 83

Slide Number 84

Slide Number 85

Slide Number 86

Slide Number 87

Slide Number 88

Slide Number 89

Slide Number 90

Slide Number 91

Slide Number 92

Slide Number 93

Slide Number 94

Slide Number 95

Slide Number 96

Slide Number 97

Slide Number 98

Slide Number 99

Slide Number 100

Slide Number 101

Slide Number 102

Slide Number 103

Slide Number 104

Slide Number 105

Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

ONR

ONR O NR

OHNR

H

H

H

[H] [H] [H]


NOH H


O H+

S

S

S

SS

S SSO

O

OH+ N H

S

S

S

SS

S S

SO

O

OH

+

N H S

S

S

S

S

S S

SO

O

OH

N HH

O H +

ANILINA

H O H

O H

S

S

S

S

S

S S

SO

O

OH

OH

S

S

S

S

S

S S

SO

O

OHO


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 13

Slide Number 14

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Slide Number 49

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Slide Number 51

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


(pero no el NaBH4


de la


una amina


4 LiH

+ AlCl3

rarr

LiAlH4

+ 3 LiCl

Na

+ Al + 2 H2

rarr

NaAlH4

NaAlH4

+ LiCl

rarr

LiAlH4

+ NaCl



LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

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Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

LiAlH4 + 4 H2

O LiOH

+ Al(OH)3

+ 4 H2

Problema


Sin embargo


epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV

epoacutexido


eacutester


luego luegooacute



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



DOI 101021ja01191a057



24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


24 3 2

2

2

2


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

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Slide Number 118

RMN ndash 1H

UV


(a)CH3NO2 NH4OAc

reflujo

(a) (b)

J Med Chem 2006 49 1101-1112




Thomas S Scanlan







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

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Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV







Nu +

XNO2

NO2

XN

N

Nu O

O

O O

NuNO2

NO2

+ X

Nu

Ph O

X

IClBr

F

O2N

Nu= =H3C O H3C S

100520340

310000088

259000




INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


INFLUENCIA DELGRUPO

ELECTROATRACTOR


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV


Vicarious

nucleophilic

substitution

of


Mąkosza

and


282 -

289Synthesis

of

heterocyclic

compounds

via

vicarious

nucleophilic

substitution

of

hydrogen

Mieczysław

Mąkosza Pure





NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 51

Slide Number 52

Slide Number 53

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Slide Number 56

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Slide Number 100

Slide Number 101

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Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



NO2

+Ph S

O

PhCl Cl

Cl

NO2

PhOS

Ph

nBu4N OHnBu4N Cl+

nBu4N OH

Ph SO

PhCl N

NPh

SOPh

Cl

H

O

ON

Ph

SOPh

O

O

HCl

NO2

Ph

O SPh

OOO H




Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

Slide Number 11

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Slide Number 101

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Slide Number 106

Slide Number 107

Slide Number 108

Slide Number 109

Slide Number 110

Slide Number 111

Slide Number 112

Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV



Reaction

of

nitroarenes

with


anion

followed

by treatment

with

zinc bromide

and

hydrochloric

acid

yielded

the

corresponding

p-

nitroarylaldehydes

in good

to

excellent

yields



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

Slide Number 4

Slide Number 5

Slide Number 6

Slide Number 7

Slide Number 8

Slide Number 9

Slide Number 10

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RMN ndash 1H

UV



Reactive Reagent

for

Aromatic

Amination

via

Vicarious

Nucleophilic

Substitution

of

Hydrogen


TMHI that

is

easily

prepared

from


a novel aminating

reagent

for

vicarious

nucleophilic

substitution It

can be used

to

obtain

isomers

not

produced

by reaction

with

other

nucleophilic

aminating

reagents




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

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Slide Number 113

Slide Number 114

Slide Number 115

Slide Number 116

Slide Number 117

Slide Number 118

RMN ndash 1H

UV




Nitroarenes

react

with

anions

of

tert-butyl

and

cumyl

hydroperoxides

in the

presence

of

strong

bases to

form

substituted


reaction

usually

proceeds

in high

yields

and

is

of

practical

value

as a method

of

synthesis

and

manufacturing

of

nitrophenols


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

Slide Number 2

Slide Number 3

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Slide Number 117

Slide Number 118

RMN ndash 1H

UV


ESPECTROSCOPIacuteA

El

alargamiento

del

enlace

N=O

se

observa

en

sentildeales

a

1500‐1600

cm‐1

las

cuales

si

se

comparan

con

las

del

enlace

C=O

en

1650‐1800

cm‐1

se

observa

que

el

primer

grupo

esta


IR

RMN ndash 1H


= 43 = 43


UV



maxmax



Slide Number 1

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RMN ndash 1H

UV

RMN ndash 1H


= 43 = 43


UV



maxmax



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Slide Number 116

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RMN ndash 1H

UV

UV



maxmax



Slide Number 1

Slide Number 2

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RMN ndash 1H

UV

NITROCOMPUESTOS - depa.fquim.unam.mxdepa.fquim.unam.mx/amyd/.../SINTESISYREACCIONESDENITROCOM… ·...

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Transcript of NITROCOMPUESTOS - depa.fquim.unam.mxdepa.fquim.unam.mx/amyd/.../SINTESISYREACCIONESDENITROCOM… ·...