the nla^e 9ll*
151
Jn the nla^e ol Glttah Eh" 9ll"* Qraeiouo {,he lloat nfteralul. 'l.Dhooe Jletp QOe Sd:cr
Transcript of the nla^e 9ll*
Jn the nla^e ol GlttahEh" 9ll"* Qraeiouo
{,he lloat nfteralul.
'l.Dhooe Jletp QOe Sd:cr
LIERAl',ha:trk ol:iiliolt
Utlo. ^t
| ! o | li t, I J J : t::hc.. tf
CIGJf, F{YE5IEAil'.
IRGOPIS
THESIS
ItZrlL. ?rr... A. I-.
tlfEtrrTr c st.mh.o
t97f
OFGLN'N
0 ,?bt'' ..'
(ii)
as!!!49!'rhe Fork desc.ib€d ln rl'is thesis c@prises of t're
chehicar investisatio. or prosoris lAililglgEgr rhe indis-enous plant betonqinq to rhe frbiry teqNinosae.
i orty one c@pounds F.e isotaLed fr@ Prosopis
extra.t obtaihed froh 6ten.nd leaves
l\$ be€h aurriet€d to nuelou. chericar ard Fl"ysicar
nethods or separation ar\d folty one fraclions have beeF
obtaihed durin. this pree56 rhich po.Bibry includ€
hyd.earhons, ste.oid8, ark.roids and .onposite oits yet
to be investisared.The physico cherical prope.ries or nany of these
rracrions h.ve b€en studie{ in deratt virh rhe aid oftnfraled, hass spectra and NL\IR sp4troscopy to estabtish
'f\is part of vork h.. renained inconcrusive due
factorB ehcounre.ed and ah extensive efforteill be neaded to .cc6pri6h the sork and achlew definirernd con.lEtve datE ln Lhis context. :lo'ever sufiicient
p.esent€d i. rhis thell€Lo extend the r$e.rch in thla field.
,iii)
)L -l!!-!,!-!-!
aratitude to il,ir, rr{) supervrsld tlirs sork
a.d h.Ipcd to rc.otrLpLisr' it ro hjs lisL
v'.id. lhe.inaLization vns frade by Dr.
.. {.zi rdr uhiclr .uthor i^ arso dratef!l to }in. il,e
nuttor is in.r.!hted to Dr. \.4. \aqvi Djrcctor, \atio.aI
in A.alvt icar .,jehistrt :.r a'ard
or rerlovs\in {rricrr trade it
th.rks are dull
to DirL.Lor, rrstiLut. or.lv'iiisrry ror Frovidi.rr.se,r.h fd.iliti.,s if rh. lDboraLorics or the Lnsti(ur.l
I o\" r..ou'J.j,
II!l Lants producc rctrborjcarlv. food $aterials
alonq {iLl' nLany othor substances such 5s ' rvcosrdes'
arkaroids, Lannins, vitanins, essentiar ois' bitter
principle. 9!s, sde of rhich aro harhful, but other3
in requlaLed doses are used as reredies for hanv
Ihc druqs obtained from lndiqenous plants
have qreat inportahce troth fr6 the nedtcinas as serr
as econoni. p6int ot view. redicinc is a very ancient
art and druqs havc been used in the days or antiqurLy.
rrm ancisnr Lihes nan has tteen usinq Drants to alre-
vjate lris $uarerjnqs rr@ diseasos, I'is sttullgle for
existanc€ dcvcloped in hin the in3tinct for sucr\ heal-
inq agents. rlrc knorladqc of healin.t aqents qrev vlthtio dnM oa civirizatim in various parts of the lorld,rn rhd rndo-fnk subcobtinent first .eords vhere the
prabts had th!: Fred@inant rrosition in iedicines vere
rentioned in rriqv.'dal, vhich is one of lhe oldest
reposito!n's of human knolledqe, hnvinq heen writteh
betvaen 45oo \ l()00 R.c. and Ayu.veda_ bet{een 2500 -
'ioo lr.c. Ayurveda intacr, i3 the very foundation stone
o! t.he ancic,nt science 6f India.
sereral other solks of a llttre rater pertod
such as rsErura s{hhita' and 'charaka sat'hita' describo
daYs ror trLldi.inar purposas.
-2-'Ihe lvurvedic svsten vhich i6 stitl jn pract_
ice in tlie rndo-pak subcontinent carries its name fror
ancienl crdek ahd lean fdi'ines tetc
iuch infruencod bt the Ayulwdic n€dicine Y'nl redici_
nrl pla.ts of the Indo-Pak subcontine't ar': hehtioned
in the totk! of .Jreat creek physjcian Droscdroidas3'
,ris rork certai.ly sh@s to ehat extent the anci€nts
€re iddebLed to rndo-Pak subcont ine.t and the East for
their nedicino, Ilany Indian plants are bentioned in
his rork, parti.urarrv the plants vhich qive armatic
qroup of druqs.'rrF snokinE of Datura in "se ol asttftt
the use of I!! !@igg in pararvsiB and dvse€psia and
the use of croLon tidliui a3 a purqati@ can ne defihit-
ery tlaced to have oriqin.t€d frm the sut'6ntine't'
Ttte scholar D@!or Shen Nunq (2?35 ts'c) of
china cdpiled a book on he(bs and is cledtted 'ithobservinq ttle a.tifeblit€ €ffects of chang sh.nq (tlF
dri€d rootsr vith 6ia11 portlons of stss attached, of
pichora Igb4llse- 3re knorn In china as chanq shanq)
vhich lEs nof been found to contaia antibalarial alkar-
oids, Ire also notted ttP iltlphoretic.rd atloulatorv
drraats oi th€ druE |la holns ( the ctin€8e n.he of
Dblidtia 4!i9!) t atiost tlve tiousand v€ar3 rater' Naqai
isorated the acti@ ark.rold
fhe aotilip.otic action of the chaalboogra
fruit uas knoHn to the ancloht rndians, and rhe &cgg-las uscd in LrazLl and the fat-iasl for
treatrent df dysentry and dj.rrh@a. Its laih alkaloid
enetine constitutes an inpo.tant druq for abebiasis.
the plan! vhicb contains thc antherbi.tic ascaridor
ras p.es.rjbed unde. different banes bt nedicino nen
of the llcbrcws (Jerusalen oak), lerjcan6 (Mexicah tea),
a.d Lhe iroans (chenopodim.nrhehinticul. lhe earl)
explorers found Lhd iouLh Aherican lndian in possessron
of cin.lrona bark froh vhich Pelrerier and cavenlou i50-
rated rhc antihar:riar atkaroid quinine io 1420. rhese
lndians.lso che€d caa-rea@s as a stibulanl and eup-
{rc use of .ert.in blant axtra.ts, .s .araly-darL poisons, chiefly hy sourh Ahcri.an
lndiar tribes hns heen rccdtnized sih.e a ton. tine. i)ne
or the active clnni.at cdoound resonsibre aor ttF act-
Doitsors has
rsol{ted Irdscythians, .nd !usr ims co.quercd
India nci oriqihat vorks uere vritt.n and the ltindu ned-
ici.e qradoally beaain ro f:rr bchi.d. Durino BldhisricDeriod3r rhouch .ur.o.y d..rtned, ftedici.e .gain oade
-5-
lnvcstiqation by L.v. AndriD" and his correaques in (ajro,
shored tfF acli€ cohstituent to tle kherrin {1), thi.h
thcy found r. he elc4ctivo vasodilator xith a sel.ctive
n.r ior 6n l.ln' .oro.ary wessals of thc hai8lian hearr.
rr@ a.cio.t Lincs thc root oa an indig€F4os rlant t,#
4f|a-se4q4!!E, h.^ bacn {idely lsed in rndia larva 3s
an antidote tf i.6ect and snare-rrit.s as a febrifuqe, as
a slihula.t to utolin€ co.tractions ahd as r sedative.
Lt is round to be useful in hrFcrtensiob and has a
r,arkcd hyDotensive action .lso. It has the reputatloi
of beinq a lra.quiljzcr and i6 used for tho treathent
cflr
(r)
or' jnsanjLy a'd -insaniry .t.tes-. rt€ roots oa
ara usad air.fr thc Foor s6crio. of the peopt€ inror reepin(: the babi* quiet .nd aE rehedi€s of;itee, reve. and p.inrui orreclion or intcstjnc.nrd bovorke.s' isolared frm this ptant a nuhbarro.d!, ^rii.,Jne (2) Ajhaljcthe (3) sc.penrjne r4
15 r. r:o€ver rlr r.st
Mc
inForianL acti!.' .d,-
, Lhe eru.idai. i.n ..
qH;
H
t.tnr s)'rthr.i.Ln ar. ira t.ror a1.aloid .hah istrY.
-1-
r{e.icyt alcohol and Pi.itol rere tsol.t€d frd
the plantll. ln tha popular fi€1d of ctetoterapy of tube-
rculosjs indi.tenous prants are provinq of Ereat interest,
llrus, Japaneso sorkets bave isotated froi I vine .aned
S!A!@Lq eebharantha, and lrd a tisteria_like pt.nt
nared s,sasakii, the alkaloid .eplr.t.ntt'in vhich is beihq
used for the lrealsent a.d the Dorbhvlaxis
chinc6e rorkcrs hlE b€en in€stl.ratinq the
antituberculou6 activity of a seties of le.l ptantsl3
a.d virqinia tanq reports a p!@inent tuberculosErti.
activityra in extracts or-goptis r99! (kpSi.g ghileEc).
'lhis activity apparentry r€sides in its arkaroid, ber-
beriE aurprEre {6).
0 ct!0cH3
T"CH:
z.ll\0tl
(e),o,{,0
lhis slF s rh.t rlch rh.i.s f.on a .l.sestudY of thc ifdi..orous herbs.
'ihe fruirs of tne.rosoly related pla.rs of
lad taljles4 and 494! liqjlE h.ve lorq bccn used l,y the
of r0!coderhzr 5.
lhc cotrLpound rutin, a vell knovn qlycosidc,
oriqinalty derivcd fron !jr!3 oraveolens has been repor-ted fron forry dirferent sFe.jes of pr.rts, i.crud_in. huck shcat, rn accidenrar disco€ryby a n.6up or [email protected] bas lead to an ihFdrtahr
in rh€ Lreatetre.r 6f rhe aft.r-effers ofroni. radiaLionlr,. thr) synttPric .r6es3es
for vhich . chenist reqrircs nidh degree or hear ahd
beihq quierly caffi€d by narure in prantsnt ordjhary.ondjLions of renperature and pressure.rrhemrst stnthcsjsed atkalotds sEh as quihine aft6.
exte.dinq ovei fifrt yelrs, clnchonaprant d@s tbis rithout difri.urty evory day.
An rre.esrih. develop@nLi in rhe recentsLudy or oidiraliE, is enphasis on jrs .cardtoronic,
rarher than on its c.rdioroxic. rlroDer!ies and tlFrclorted dls.ovory of a ne, orrcoeide di.Jicorin. thi6lyc.sjde "hi.h has tow toxj.jty, is cr.jned t, Fossess
acrior or di.icarjs disti-.t frrn thar .f
qrYcosides {hich
rt ca. b. extracted froh th.
a"d qisgi.!-e1-!5 .I-3-!3!.a'
are rarqetY cardiotoxrc.
teaves of q!q:!.n!-E !!!rg!sE
on the a.lhraquinore 'rouF of
purdatiY€ drurs ha6 shotn the inb'rtance dr the foft
in {hicl, the anLhrarluinone rcur ir the
satisfac!.ry cheoi..l and biolo.i.ar rethods of assav
lhich havo been dove!.oped 6ho{ lhat the antnracene der_
ivarives a.e hi.hly active as a. Anth(..ol oltto3rdes'
studi.s of !hes. lihcs rade on ec4!8, !!!a!! and a.!-gcs
te.d to clarily tlE exact naturc oftlE aclive ingiedie_
Dts in these d!un5.
It is .trrious to note thal soho 6r the prants
ha/ir- r'.n1r'cbIy por6't a.Live Dr'_'lDrec' orocinc
side hy sirle qjth the otherc, vcre rcfl unto!'hed i'r
exnnbro nn noti.e lLer.l-eg9!a, lpled-lrt.llleEis! 9!S art of 'ni.h oro, sjde bv side s6ne
"thase very prarLs eere uLirized hv tt€ chtheso and tne
arahi.n nedic.! iicn oa the.offes.dndii. Deriod rilh
cons!d.ralrle success
rith thc advent or '{estern i'€dicine th€ in-
quisitire rind ol tlF ci.st€.n schorar8 b€gan to eork
on the lndian nLedi.inal pl.nts. Ihe sludv of rhdjan
i.dinenous dru.rs vas first bequn in the earrv p.rt or
-lorlle l.tlr.o.trrey'- and vas at that tin'e cohlined hainLy
Lo the corlmtjoD of av.ir.lrlc irformtion re.lardirq
vdrious ncdi.inat plants.
,{lrcn Arahs caDc to India, Indiah nedici.ar
Dlahts st..rcd rE.oninq intoresti^q to the luslih .ra!ins(Aurovedic doctors), rhejr use ie.ched the clibax durind
{udhar Deriod. Durihc and alter that period lndia has
prod{ed nreat rlakins like }ra}iii ^jra1
?}an (ho shdod
rhrt rc.l .rants conr.in.nd D.oduce vhac hodern.hft,istrt is sirpry Doverle6s to dullicate e@n ir the scqr
uDt.daLe tah6ratrr j.rs.
.onscq@nlry, durin, raFL fey dccadaF ; .o.s,.de..bre i.ler€st [.s rreen evoked in rhe sy6tcnatic cr.:F-
icar ihw.sti.ratlon of pl.nts a.d reasonable proqress has
bceh r'adc in this rield. Andrip 9! 3t,r..J.atu s.D, rijddiqri, Dyho.k, '{arden, ooper a.d,nany o Ervo.kers have establlst€d boyond a.y dodtt rhat one of
fi.lds o! eonony ot rbe sulronriheftr.hains uhcaFlored and u.lwsrirtarcd ubtir ro{.
'rhe medi.lnar pt..ts fc!tr ,. ihForrait D.rtor Pa'<istnh i'6qetdtlonr rhelr rrdror !tjriz.tion and
de@ropreFt is quitc he.aiary ao. proviitin. chea.,:r
llEt dr Dr.nLc s,ipposcd Lo have hedr.nar v.l!o exceedr l5OO epcics bur h6sr oa the6 aro
i-
-11-
r.c:r iirr.rra..e. Artmisia oat j t ina {sa.tonicar ) Idlgllqqs4!! /rna:), |altolria serDe.tina, A.!r!js!Elj! -9-l!!-
.!.f9!a, l-*E:E!!l !i-!43!LS are som' or tl€ bedi'iial
plants oi rhjch or(Bniscd atletrrts
Lhjs asFccL dr our.aLir.ar {ea1th'
lhe aore ikportant scdicinal prants Yhich
cdlriva!.d in Pakistan are eilised as under'
!-r3Slrg .I]tp.a.g3.gn ( 0 round nuL ) ' ll!3s€-!.q3 99rE-!!!l-9
(sarsoi), rrrassi.. iuncea (il.i), e3!]Flgsts 34!q (cril1i's)
!.i4!!g gtEri (.aravay), carica babava' curcuea 19!94 I iur-
heric), qg$tssl!! 9!p (cotLon), q!!4s g!Elr!g!l( ora"'c J ,
cor iandr!f, sar i vum ( cor iandcr ), !gedc!.]-c! !!.I!4e(r,cnner), !-:!- !:i!eliigi!l]L( Li rseed) ' rrosadaFra !ee!3
/.ose), !dg:g! splllr{elslu (/)bi'ri! r.brylj^ variols narts or l,akislnn
r., Lh. faturar lrorn ol Lhis reqi"r spi'e
'rportart !ridicinar Frants like (.rartaoo 9!3!4),citruruscorrvn ,is r uM). qj:sd? aunqustirolia (se.ra),e-bg!a-
podiun n!:It!Esi3g! (nori se!d) arc .ound jn thi6 relaio!
{nicI alor.t{ith oLlci drouqht-rcsiscanL tedicdl plants
like \r@ \:(% lxun!'ar aandal), crrcvrrhiza l4-CEe't4,iyi!!j!g! rar rie,ro*n i' the so carred,aste lands lhus
er!!!!"I!S colecvnthis.an be qrown in thE sardv de6err
tract virl: dorlrlo b.rafit of croducin' varuahlc fnrrts
a.d nindir san.l drnrs. ri lh. for..t Dlantat i.n 6f :\it
-\rr!!l-i !!a!j!3, 4.!!cz4i-e r-gbD!!l!, !-il-e.!!e!l-:
!!-eeg!q' --aitsi-a .!.!.e!.n!4, c-e-!-E!4 lr-:!r:.},q' !4-!rl-LqE
a:.r-egr!lr:. 4-2t4!5 jgj!!3 !91348 xanlhtrarou( 9!g:jre a fov cxa.Dt.s or tle D:ants *r:ich are lrein. used
fo. nredi.if.r .lhoses in siFd sirce tiic inrenoriar'\ecessity ror research in identifyi.q and
isoratino jndi.cnous druqs nas arlsen froh the ract
riar ouL of rhc rar.'c .urber oa druqs u*d by lhe
inverajes aft i:artins for lLany centureis, there are ra.l-
vhich deservr Lhe reFulation tiey have earned as cures.
hislory shovs rhat n,aDy of our ifrporlant pharrdcoloa-
ical dru<rs r.rc lsed in soB! :-oin .r the
ly ronc b.forir they were i.trodu.ed int. the '{estehnedicine and bofore lheir ..LiDns {ere irvestinated on
r.ientifi. rines. trh the othcr hand tlrere are defiFitelyorrErs o. rittrc fherapc"ti- varu. whi.i ar. h6rery
.iv.. bec.u<. thcy are nc.tio-e.l i. so.e old na-us-
crirLs and n.) d.c has taren i.lie troubre to co.rirn tf.auLhenticil! or lhoEe statcronls. tj.cnrse of Ll,js. sdtr.
the <oods ones rroh t}lc less use:rl
ones and for this a systeiatic investi,ration of rnese
druqs rhust he und€rtaken. a3 thd chebistrt of planis;dvanc€s lt vjtl tnere js d very qood
thci. use and sse say Frovc ever suFerior tt
syrL\e!i. drlds lsed todaY.
. varios rab.ratorics
iques, ssh as eretrolhoresis, thin \aver'
and wapour phdse chrotr'aLoqraPhY,
.tion qlq h.ve been found to be or llreat help and have
l€en very r'alcctivefy usod in the seperaLio. ol' conFrer
of these tehniqDes isorat_
ion or !orc and chrohatoqraphicalrv seralab!€ substances
froh a usuaLLy irtractatil. co$.!ex nixtures of- Phvsro-
rTically a.t.ivF consliruentF lras hecone relativelv
sin.le as .o1.n!.d 'iLh tha orthodox pr6edu.es, cnFloved
durinq enrlior days or resear.h on t€dicinar .lants' the
hosr nodern instrunrehts such as lbfra_led! I ttra vioret,
ru.Ica! ra.rnaLi. reso.atco spc.trophoto
dt., hav. ftr!hr. 6iiiplified thc.erocidar-
ion oi Lho structure of co&Dou.ds obtaihed fr@ prants
i.toin: in vier abovc nentioned putFose a $heF
vas initiaLcd in the year lq(,', in lhe InstituLD or che-
risrryr fniversity oF slnd, by Protessor )1.t\, iazi. to
rind out tl,. ictjve principres, of '"lF cmron nedicinar
Era.ts or :iihd. this vo.k is in conrintation or the
iine .ro.rdnre. The york descrihed in this tlicsis i.vo-ries tlre r.h.iticaL inv€ati(atior of Pr6soFls dlandur.sa .
LlraL, ia tl'o vork in ris fjord is conLinu.d
j!6, Ieaves ahd florers of the pl.nt tere
scperatcly dfied under shado and .ut into sn.1l Ft€e3..acb baich l:ns cxtracted fit3t vit\ petroree ether
rotlolcd hy Lrnzene, etlvr arcohal. the
rurDose 6r cxrra.fin- Lhc llant vitll the:b.ve hent-
io.ed solve.ts n6.-rorar a.d seni-
.ucn as hydrocarh.ns, essenLj.r oils'steroids, tcfr.ncs a.d liDl<ls aroh porai.ohFounds,
Ijk. s!-jn.s, ardchydcs. ai:jno acids, afiaroids, frav-onoids cL.. Ih! forfrcr .roup of .onFo!.ds is soluble
in lonpotar solvcnts rikc patroleur ether! b.nzene .nd
thc rarcr are sorublc in polar sorvents sEh as r.thllnlcohal otc,
I I' \in r,nvc._!l.r!9!a!99M!r.
L ri. p!'Lrolem ethrrr, bcnzeher
ethyr alcohal c\tr.cts of and tro@rs
vere tested by thi. rayer chrotratoqrlDiy usi.q a vide
varipiy.l s.rvFris and sorv.rnt syst€h6. tht. gave a
rougn idea re9.rdlng f,lf nuhtfr of c@ponentE ln eacll
ertracl nrd tlE .)nss of conDounds. It also anabled D!
the ddsorr*nt nnd the elrtjngcrruh chr@toqlrFhy.
-21-
l. Ih thc ole!'ent det4tion tcsts oxyqe. vas aound to iepre-^erL hut tlre haroqons, nitrqten and sulphur vere rot
indicaLcd,
2. Pros{:f.! ol hydroxyl rroup {as irdjcatad vheh tl,. conrp-
ound nave positiw test vith fefric chloride and ceric
nitrate. ihe Inara.ed sD4tru also sh(ftd lha character_
stic i,and f5r hydroxyr qtouo. Tests vith Dotassiun Fer-
ranganato a.d br@in. i. carhontetra.nloride tere neqatiE
co.airftj,i. lJre 6atur.Ljon ot rhe.omFou.d. 1nc Infrared
speLrur of tlre corpound also indicate the prcsencc or
l. lt {as rourd to lte ar@Lic, rt shoved positive test
rh€! subjected to ! riedel-4rafts reaction and for!'atde-
hy.le-sulphuric acid tast. Acetyl derivative vas arso pre-
Dar.d shovjrfr Lho presenco or a hydroxyl gtoup.
n, lhe rtrrfarcd spectra of cdhpound z-: and iLn a.rLylderjv.tjve vere re.6rdod uBln.r {ljr discs. 1he Dosltioroa ahao.rJtioF Feals and cneir bossible tnterFretatjora.e qiw. iD table lI in exbarjrertar.qa!49!!LZ:: .
rhis.ortFoufd (6s ohtdjncd as rniue shi.in..ryscars. lt ras freely soruble jn r.rrroreue erlFr,tor.ene.ehtorofofn; cdrbontctrachtoride a.d i.soluble in eEhyr
alcohol! icthahor and vater. Lt * '"lkd .r af.
I. ih the Flene.r detFction orylF. was fdund to be nreBent
hut tlle )6loqens, nit.ocen ard surphu! vere .ot indicaEed.
of hydro\yr drou. vas indicated vhon thc .onp-
.und gave nositjvc tesl rith rcrrj. chrorjde dnd.cfic
nitrate, the Inirarod spetrum also shryed
jstic band for htitroxyr qroup. lcst rcr the
calbonyL qroup ras neqativc, Arthouqh it did noE dtolon-rise dilutc pot.ssiu pe.nanaatc and brohi.e ih carbon-
Letrachro.id.r, tha lnfr.fcd spactrur inforred the preFence
or a double bond sbovinq C : c slrctchihd vibr.llon nt
laaD cn-l a.d ars. :rm the nDlo.ular fornorea of thjs
1. It vas found to be ard.tic. rt sho€d positi@ te6t
rry:. subjcct.d to Frioder crafrs .eaction .rd aorr.rdeh-
ydo surphuri. a.id re.t. It aave positive li€b€rnahh
Itr..hard r,rd s.11kd'skt roa.tions ahovjnq it to bc a ster-
4. lts rolecurar fornulea C2.iiro o contains ten hydlo-
than a strnih.tt cnain saturated alcohal.
ilris eas llstiiied by Lhe racL tnaL ttF c@pound has
rour rinqs ard a doubre bond.lnf!.red sb{truh
Inarared Epectra of sL'rroids and triterrrenolds
lDvc been studied very exrensjvely. rney Form an ideal
con.ounds for rnfhred slddy sihce they
,!
lho priMary an.l sec.ndary methyr qrotFs qllcdour,rets ai,d trifLets due to couplinr vtth flethyrene and
relhyne srouDs respectively. As the aolc spectrm ras not
scll rescrved, it yas tharerorc diiticurt to hak€ proper
^ hrodd rtrD aL c =I.r'
to protors directly attached to tlre
pentano.honanthene hEIleus_ and a
due to an otc.inic proron.
7, re c.nFoun.l sas.ha.acterizcd as9-sitosterol from
its miaed FcIli".r Foint virh rn 6uchentic sahore and.lsobt thin layer chrosatoqraphy of Lhe rixtu.e oa conround
z-s ahdt-siLosLeror. Ac€Lyr .ierivarjwe or z-.r (as arso
Jrirjrar ro Lhosc of 9-=irosre!or (7).'rn! jrporrant r.n rrio.Ls sho{n ir tho rabr. r!
crP expld'r."r d\ rnd, r.
Dre rost prnhahly, -15r .-llt a.d I -ll
- 2.5 pptu ia attributedpeihydro - 1,2-cyc1o-
conprex at 4,9-5.5 is
l. - l.1l (c1ori21, side chnin) -,--- 2?.j(21?') .
?. )r - t5( (ctor21+H2o i.e. renoval of a vater nolecular.nq rith sjde cl)ain) ---- 2t5 (4o f).i. : - l!3 (side chain + 42 mass unirs, cat:r)) -__2-tr,1?.)l.n,ovdr o. .rd-.har. bluq 4'rn\. u.irs isino paiter. in =teroias24_?5, lhree.artrorF if this ,j.ir
5. l + ,,)
-2 )-
o: ste.oids h,c sho,n that it is posslhle
!o as3oci.te certain bands to sFecific tvpe of structlre'
i! has beln r6und t.h.i the reqlon berot 1315 cn-r js
usoful For r4atin:a lrydroxvr qroups at c-3, c_5' c-17
and c-2o rosi!i6ns?t'. fhe nost Froninent band in tlre
3-hydroxy sl€roids -curs in lhe ranqc ro5L to 99' ct-l
vhich Droves that n-li qroup j6 at noEition 3. Tnl6 band
aid a ha^d rt lO2O cr-r sloF th.t ri.qs A/3 are tra_s
a.d cjroup 1-l: js preFert al- 1 -r)}l .nd tho c-o band is
q9!.p.s.!:d ?,--l-{1.
':his cohpou.d sls obtai.ed in the f.rm of a
yFrrosi\h oil, lr uas rreety soluble in petrolFUn
erher, b6nre.e, carboh tetrachloride, and insoluble i.ethyr aceta!.r, rethanolr n-hexaner etl'a nol , acetoi. et?,
Lr ,s bojred at 220e. lrre physio cllenicll slqdles fort\c chara.tarization of .ohpoud Z-lO rere perrorrad
I. In th. elmcnt detrtjo. tests shovd that nitrogen,
harogen s!rFhu., vere ab5e.l, huL orygen {a6 round to
2. presen.e o. .arho*yiiF nroup v.s indic.ted vncn the
conpoond qave iositjve tetst rith sodjur bicarbonate.
llre Inlrared spelnb atho ihored th€ characterEtjcba'jd for .arhoayrj. ..oup. ;\tthduqr, it did not de.olorrnsg
-2.-dirutc .otassi,r and hrohihe in carbon tet-
ri)cnlorjdo. ti.c l.f.ared sF.rLrun: iirerred the bresorcc
o. a d.ubrd bo.d shovi.. clc strelchjng vibratitn at
r. lr. arorari.. lt sit ed positiE
Lest ,hef .xrrjecled to rtieder-4.afL reactio. and fo!-
maldelryda sulphlric acid test.4, ihe r.rrared spe.Lra of i,-llr vcre recorded usinq <t,!
djscs. The posi!ions of lbsoftljon bands and possible
interpre!atio'r nre presetrted i'i table 1r
'-g!1P.9!!4 lif!ihis .o!'p6urd vas obLained
yelloris\ oir. lL uns f.ec1/ :iolouetrt.dclirorid., ard i
.-hexan4, eLl,anol
v8 hoired aL r^oe. rhe phy.ico cl,rh
r h. .lrara.Lcrizati.n o. coirn.ud 7-1
in the aorb ol a
in pettoreu other.
1. Ll.nc.L dctecti.n LestF s)rored rhat rttrdge., haroqen
arrd surqhur re.e abseht, hut oxy.reD ras found to be
2. Presence or carboxylic qroup ras idicated vhen the!.
corpolnd liave positiw rest {irh sodiuh t::carbonarc.
the Infrared shored Lhe charactelstic ba.d
for carboxyrj. .Jroup. AlLhough iL did bol d€corourlse
_tl._
dilute potassiuh and hrorihe in .arboh terr.ctroride the in.€ff€d xne breseice
. a d.Dblc b...1 shoqin. c;. srrerchir^ vib.aticn at
r, rr yas .ourd to be aro!,ar.i., rr .nove<t oosirire resrvhen slbrc.rld tD rriedel-crarL reaction and aor4alde_
iyde - sutphuric acid test.4. rlre Infrared sperra or 7-t2 vere r<orded usinq,ijrr discs. lhe posirions of lbsorprion bands and possibrc
rnterprecntron are pre6ent ih rabre rr,cohpourd z:Il.
ixrs coitrouDd ,.5 obLajned in tho rorh of yetlov-ish dir. rr ras frery sorubre in petroleu cthei, bcnza.e
carbon terra.ito.jde and jnsollbre in ethyl acetare, bert,-ethanol, r.ctone elc. rr tr boired at
to42. lD Dhysi.o .henicn! srLdi.s ror rhe charr.re.izatti.
l. areE€nr detecrion tesrs shoycd rhat halo(cn .itrf.or,srrphur re.o ab6enr, buL oxyqcn ras prcsent,2, rroso..e or carborytic qroup ,.s indicatcd ,neh thecdhpound lrava poEtiw to6t {jrh sodi@ bica.bonate. ,Ibe
cl1e.l&-!5.
.arboxyri. oroup, Althouoh it did not decoloDrise dirure^ e.-hE..d brort-etrP(r. chlo. id. the
l.frared sDocLrum j.rorred Ltje , doublo bond
qgrroud r-14.'iiis.o$pound sas ohtaired 's c'lonrless 'rvsttr6'
,t {ai rre.ry sollhlo ih pettoleun 'tfer' b€nzener chlor'_
rori, rfd.nrr-'o' Letra.hI'ridc, a'd iFsollt'le in a'etoie'
cthyl aceL.Le, at ?qo to 8€'
the physi.o cheNicar sLudies rdr Lhe 'ha'acterizaLjon
of
corlou.d r:-lJ u..c porforr,ql extcnsjvely
1. 'ir.merr dcto.tion losts srro{ed lhat nitroqen' halogen
nnd sulphlr found to be FreFenr'
2. Pr.s.nc' oa l:ydrcxyl qrouF las indicated vhen the cotLpooho
.awe Fosjtive LrlsL {iL)r f.rrice chloride abd ceric nitrae
si..rrrrt also s &ed the characlersti' hnd
ror hydrotyl of carboxyl orow
{as ne.ative, Irtl.ou.h it did ..t de.olouiisc dilule po!-
-ssiun.cr,ra l,nr!at€ and brominr i. carboh tetrac}]!o!id''.
tlie rnrrarl.? inrerrcd tne Drese.ce of a 'loublebr.:d sholiri .-i strotchi.., InlT cr-la'd a13o
iron rlro nolDcular formulea ol this cohpound.
L It qas aoun.l Lo be non aroratic as lt did not react
vhen subje.ted bo rieder .rar! .eactjon and rori'aldehtde
sulplrdri. abid test,4: rhd rnfrared st€.tra oa z-14 rere reotded usins iiB(
discs, ihc Fositlons or abgorption pea*6 and tlieir Fosbibteinterpretatjon are prcsent in tahle II.
lgmoornd :?:IJri'!,i!..xnound Fas ohLa
crysrars. , wns 'r.a:ry s.]uhr. i
.arbon disulrl\ide, l)oL n-hcrane,
acid, slari r' ry soruble ii ..rdjn ethyl acctaLe, ethyr alcahol
sorurion, rL N rartcd at lac,8.
sLudics ior Lr:' .hnracLc.tz.tio.Dcraornea .xLr-.si vcry.
ired as needle likc. b.nzene, chloroiorn.con.ertrared sulDf uric
.-hexane and insoluhle
a.d sodie hydroxjcc
'r he physico.heni.:loa con'pouhd z-15 rnrc
l dlfrrnr d.LFLion Lests shded lhat oxyge. sas found
Lo be prascnt ruL the harogqrs, nitroqen .nd surphur
selo ndt ifdi.ared.,, Pr.se..o . hydroxyl qroun vas iidicat€d vl:en Lhe
a.sit.ive test vjtt rrrti. chrorid. ad ce.icriLrate. iic :rrrrrcd spectrua arso sn@d tlE cnarncter-sri. ha.d 1,'r hrdroxyr .;ouD. idsl for the pre*n.e or
.a.honyr ,,rour v.s rc.rativc, attlror/,h iL did nor dccolou-
riso dilut.r potassiun Ferman.anaLe and bromine in crrbonLclra chl.r id., th. tDfrared .;Fecrrun inferrd th€ Dres-
.nce o. a dorbte bond shovins c=c strerching vib.arionat 1{,25.r_idnd arso fron, ttra nole.utar rorrutea of this
3. It 'as fou.d !o bc aroraxi.. rr shovod posjtive tesL
shlqhcf r')hi...r?rr ro Frjcdcr-.rarr .ca.tjon and forral-dahyde surFrrurjc a.id resL.It.ave bosjtive lieb€rrar!-
iLio.s o'absorDlion pcaks and
aro present ir !ab1e I(,and id€ltifacti.r or co.For.dB
1espg!!q/i1.rhis coflpound va6 obtai.ed as colourl.ss .lyFtals,
rt ras rrcely solublL' in peLrorem eLher, 'rrzcie, hoL
n-hexancr hot .hloroforr and ins.rubl. in .old r-h.xane,
a.atona, cLhyr alcahot and bcehanol .'tc, It ]6 le1ted at
561 rho nrrysi.o chcnical studies ror thc characterization
oa conFoufd z-1. vcre perforned cxtonsjvery.
1. Elonent deto.tion tcsts slrosed thaL nitroqer, haldqen,
a.d sulrnur {ere abscnr bur ofyqcn raR aornd !o b€ p.es€nr.
2. Presen.€ or trydloxyr group ras ihdi.ated vl,en rhe cr$-Dound oavc positiee tesr rlth rcrric chroride ahd cerjc
rnrrared specrruh arso shded the..har..rer-hydroxyr group. lcst ror the
carbontr group ras heqativc. irrnouqh iL did nol d4olo-urisc dirute FoLassiu perianqanaLr and trror rne !n carbon
t|)r: rnfr.rod specrrui inferred lhe proE-
hond sho{ino c=c atretchinq vlb.ationaL lr74 .F ' d.d als, .r4r rh6 lol6cutar rornulpa o. Lhts
isorat.d fro.: reavos,
l: It vas f6und rd he aron.ti. It 6h6eed Dosi r irc resL
-4.,for tlE.l,.r"cteriznLio. ol conpound z_24 vere per'orde'd
l. ilenienL dctec!ion test.s shoved thlt nittogen, oxvqeh
sulphur ard haroqens ,ere absenl. lhis shoted that the
cohpound ijr , hydr6drt0n.
2, (len€:ral ronnur.a ror tlrc saturated aliphatic hvdro-
c.rhons ic crrl,n+2 rlolccurat rorniulaa of th€ conpound
,1-24 is in a.roeh.nL vith thc qenerat
{tcd .y4r'c1rro <. .sr< diL\ oo -ssjuh
and br.ninc if ca.ho_ tetr.cl'lorido solutro. vere _sat_
ire, co.rj.nin. rhe saturatio. or tha conpound' lhe
rnfrarcd sFc.tr!'tr nlso did not indicate
rhe p!es..ce oi a y d.uble bond.
'J. rt ras,r!so co.flrned that th..onipound z_?4 is a
sr.aiebt .h.in saturated hydrearbon as it forad a
urea lncruslor derivalive' rhi.h is pecoliar to straiqht
chain hydrocarhor!".
4. The rnarared speclra of the corFolnd z-24 and itsurca in.luslon aomplcx we!{! rccorded usinq {tr di3ca,
'Ilie pdsiLiors of :bsorptiotr Fea\s and possible int.r-prcpreraLjo. are prescnt in tdbra lt.
!-a!P.q9!C-Z:?5:',liis..irDouhd vas obtained as vhitc shininc
crtsrals, rt *as rreely sorublebenze.d, .hrcrorori, . horane, sF.rtnqly soruble ln
;a
g
I
foi
g
3
i
9
a
H
;ll
io|;
s,
t;lt:'Iq
ti
\\/.9
:"!
!al
o,.l-alo9l
:-li;l
r:r
1q
q
;
I
98
iE...
;rl
;.1-sj-l
!
ii6
_.fn6
P.: ?.:
9 I S90qloS9'4 e: :.:--.:"-i: 6 69 { { Fgi 4!- a 4 ! 9e! ! !;ot'-l! "d
, ".t"rc" 9i i'3
E 6 E E F .' '
F F I F F E E 6 E
3F 8B 3 R 3€ 3{ 8883 tE6ts ;it d ; c s nn nr -
l-T.i
I
I
Pe
9ilofa4ac
I
ll
i'?
l;
?
a.t
F55Eti,at iaisi s'ii;ii ti; i;
.rtEt' trt6 trt; ar ari tr t, tE tE t6 t6-rt6
ail ag EEq HP gE Eq I E;F
ra'
?
i3
!
-i-u4q
a
:.
;1
t;i
;l
;lI
I
I
q
:l ?
.i;;
a
:;
9
:
a
lrllt
6
g
I6
6
5
6
ai
d
d
6
d
d
d
6
5
,",h.f
d
d
d
d
6
d
d
I
6
aId
d
B
g
E
a
6
d:.
:
7
5
5
5
is
5
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6
d
5
d
E
,f
i;
i5
d
6
ii
6
6
5
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6
6
a
t
I
6
6
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6
6
6
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t
6
o{ cq
Y4"'t
6
t
d
6
5
5
d
6
ii;
B
$
6
d
b'
6
5
d
5
6
I6
6
B
5
6
6
dIti
d
6
5
d
6
d
6
I
"" .t'x9.; ol
6
d
s
6
d
E
6
d
5
5
6
s
5
d
6
B
5
d
d
6
-,$
6
5
5
I6
B
d
6
i*
d
5
i5
6
d
5
6
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d
,.1
s g!
ixlra.i i.n o. thc steh. Icavc.!rq 11!9!e!51!_!r!DIrn! rrosnnis-rrandrrnsa.
lii), rxtrr.tion viLl, hnnzer,a.
hc extracrion las pe.forned in dirrere.!
solvents in the rotl@tnq order.
'i). Lxtraction ,ith belroleum ether.
ajr dried plaht sten (l?,o3ll ks) vas cut into
shatl pieces and lerluxed {iLh rith petroreuh ether
(60-uoo) ror about three hours. rt vas filt€red .nd
the residue was \ebi for extrn.tion vith benzene
(d.s.ribc<l Iata. ). th. petrol.xn
.oncenlratd and finalry evapd.nted. the dark qreen
extract Lhus 6btained {as rane.l as bet.leu$
,h{r resid!e nrtcr .rr raction ,ith p.tror.rrt
ethc'r (described ar,ow) ,as .ofruxed riih .ohnercial
about thrcc hours.
lt sas filiered nnd the residue 'as kept aor
extraction vilh acetone (de6.ribed rater). 1he banzcha
concehr.ated and finalry evapo.ated, lh.greenl€h 6€hi-solid producl thus obtai.ed tas na&!d ,s
-74'
(iii). lrllnction {rth a.etg!q'rhe resideu alter ex!'action vith benzene
(describod abov.r) eas reflurod tith cNerciar acitono
for about three hours. lt va' filtered aid
vas kept for extraction tilh ethvr alcohar (descritreil
Iater). lhe eas conc€ntr:ted and
fin.lly evaporated.'rhe d.tk brovn s4i_sorid product
rhuE obtained vas naftt as E99!9!g-9I!l!9!'(iv), Exttaction tith ethvr alcohtr'
:he residue after extraction {ith acetone
(described above) va6 refllted *irh cMercial ethvr
arcohar ror ab6ut th!€e hours' lt vas firtered and Lhe
resldue {as retain€d for the oxt.action
'lhe e:tract tas concent.dted and finarlv evaporated
'rhe dark brosh qumy eitlac! rds naGd as CfggIELig
!_ror sheet dtaqran
ion or cohpound6 rroh d
have been srniar ised i
oa the exlracrron ano
irr.rdnt parts or the
n tabr€s 15 to 16)
7
:I;l.;l
',.
li
-.
-i
;
;
I
-
:
!
1
il,xl
;11
-ao-
9H8..
-!i- -
I
;
.-
-82-
E
tlbl
3
L
i
il
J
:l
l
-65-
I! -t ?
5b;!l g
; : -"{e
ti: 3
e6;;.9
idsit"-6!3'!g
(a). $ceerrtion and isolation of the conBtitElrts9!-!Bl!9!c-s!!rsEl
Petrores etlEr e*rract.TtE petroteE er.he. exr..ct (246.6 gDs) of
the plan! 6t€h vaa disBol@d in nlnlbd quanrity ofpue t'enzene a!*l .dsorbed on a cotun of aitica-qet.lt vas fi!3r eluted rith perroreu ether (B.pt.6O-aOo)
aolloved by benzene, chlorofor. aid ethyr ac€tateEeapetively. F!.ctlons ot 25o nt Fre cott<r€d.a.chrractloh sas subJecred to rhin tale! chrdatosraphy abd
slrira. fractiqa Fre .ixed toqettEr.variou. flactlon6 rnich sere ftn.rly obt.ired
tn different etu.nts ale qlven ln rable t?.
'corour of 'N6ber of 6pot3'60rution ' in each fr.ct-' liEr-
r. ( 1) r-2
l2) 3-4
(3) 5-6
( 5) o-lo(6) rt-ll(7) I.l- !5( 3) t 6-r7
!!. 1r) l-212) 1-4
rrr.(l) 1-2\2) 3-4
{4) ?-arv. (r) l-2
(2) 3-5
Liqht yelt4 sirEle apot
!iqht yello{ Sinqle spot
Liqht. Yell@ sinqle spot
Li.lht Yellov f*o apots
Light yerr@ sinqte 6pot
liqht yerld Sinqle spor
Liqht yeuov sinqle spot
Liqht Yellov sinql6 slDtYell4(da*) Three spors
Yerrd(dart<) single spor
Yerroq(darr. ) sinqte 6por
Yel!@(dark) Ts apotsLisht Yellor singte 6potLiqht Yell@ Tro rpotsLiqht Yell@ Sirqre €potLiqht sreen Tro spols
Liqht qren tso 6pot6
-39-
rrracrion l, obtained on orution rith berroreubether rheh.lr@ed to stand :r roon te'p€rature fdr24 hours aave shininq.ry6tals, 1he sotid haL.rjat {asfiltered, re.ryst.lrized rr.h petrol€uu ether tH,!, 4n 602)and then dried in each. lhe conpouhd, har*od as z-2,
l( qas.haracrerized as ,olrdvs.l. sorubirirv tesr,
o. runcLional groub and n.p. see rabre r
cofrer.x of z-t rcsby th€ usual nethod and lccrystatrized arorl
Ir vas fou.d ropetloleum ether, behze.e,in acetonc and ircoruble
be readi ry sorubl{r in n-reYatre,s-a.i .1y sol ubrc
in ethyl a.erate, ethyt-at.ohCr
ion vjth FeEroreur
frF trrrared urea .onprea oa 7 ?shoyed absorp!joh at t441,:]:Jll,2q50,28?o,t.so,looo ch-1
spectrum of conpound z_2 shtucdabsorptioh, ar 2n50, 1465,?lo and tla cr-r yhich i^cha.ac!€rstic of an ariphatic sarorared nforea.bon.'rhe literar!.e survey shorcd thai this cohpound h.y bc
hence z_2 ,as cohpared ,iEh an authehricsaopre of n-nonacosane {1hi. ray.r, rnfrared specrrd.mixed nelLihq poinr). lr {as fi.alty concrudcd lhnrcmpound z-2 is identjcar vith n_nonacosane (j,itl'1,nerrrne poin! or D_honacosane is 62.12).
rractjoh 2, obralned on elutotber, rhcn arroved to stand at 106shi.i.q crys!ars, .fter abour tvenLy
solld nateri.r vas riltered,rerystarrized rroh
pelrolem ether (lr.P. 4o-bo3) and th.n dlied in
'!he cohpound harked as (z-3),helted at ?c3. 1:
It {as characterlzed as foltovs
r. i9l!!.!11!y !e9!.It vas foubd to be readilt soluble
oreu ether, benzen€, chloroforn, sparingly
in acetone and ibsotqble in ethyr acetate!
arcohol, nolhahor and {ater.
an acetyr dertvalive ras pr€Dar.'d2q.nd
reystarrized fron ethn.ot .r. r343.
'lhe Inrrared the .ceEate deriv-
ative of 7-r shoqed absorprion at 37oo,31oo,1500,t400
cn_r. fh.' Inlrared speclruh of .onpound z-l shored
abgorption, at 35O0, :Jl25rt4lro, 1190,720 (v) cn-r,
or run.tr^nal qrDUp ind {.P, sFe rcble l.
2. Prebar.tion of a.etvr derivative or 7 :1.
I ra.tion I obtained on otution vith Fet.roleNether vhen artovd to srand for twenty four horrs, ar
q.vo shi.in( c.ystars.rhe solid ras
firterad and recrystauized oth.r {,r,1',
4o-.,o2)a.d dried in vacm. lhe conpound rarked as /i:r),
Lr !Js characLeri2.d.s Forlovs
_9I-
1. Solubilitv test,It ras fourd to be r€'dirv soruble in petrir'i'
oles etberr benzebe, chloroforh, calbo' tetltchlor_
ide and ineoruble in n-heEne, ethvr alcohtl' ethvl
acetate, vat€r, hydrehloric acid
l.or functional group .nd
2, PreDarar !on !!-?r!--dj!lL drlz!ne d4riva!L-
A 2:a dlnltlophenvr hvdrazoo ta6 prepa'ed
and r4lys$rrised r!o! ethanor' Y.P. l2o3'
The Inflared 3petrus of 2:4 dinintrophenvl_
hydlazone 6h@ed absorptlon at 3loo, l6aor l4qo,140o'
8oo, ??5 cn-r. The lnfrared colpound z-6
shoted ab60!ptiob, at 3o0or l?50,1640,13a5 cn-l'
I raction zl obt.lned on ertrtion ,ith petsroleu
ether Eho{ed the presenc6 of l{o conpounds. T he
blrture v!6 sepe!.t.d into its c@FoEnts in the
folro{inq hanher.
a coment.ated sorution of this lractlon tas allded to
srand at r@n tdperature for about trentv four hours.
A sorid et€rill crt6t.ttisd out, vhich eas filteted'
ershEd xlth n-har.ne.nd retyBtallited fro!. trixed
solven! of n-he:.ne and ethyl .Icohal.1he crystalllne
3o1id ,aB fou.d to be chr@lographicarly (benzens
chlorororn and chroroforn) pure.
-92-It vas barrred as z-s (M.r, 136 -373). rtF hoth€!
ltquor, arLer the .erovlr or z-a and the vashtnqs
lere cmbineat and concentlated to near drynes6, lhinl.yer chrdatoqrtphy of tbts corcentrates sheed thepfesence oa one iajo! Mponent fith other ntErilpurities. It eae therefore subjeted to coluncht@dtoqraphy (slric.-qer) usinq petroteM etbcr(8.P. 4o-6otj as eluant. the fractions containiisthe najorf conponent vere six€d, corcent.ated and
left at rom t€nperatlre. Afler about trehty four
houls, a vlrite solid cryBtalllz€d outr rhich eas
fllte.ed, vahs€d rith n-hexane .rd rerystallisedto qive needre - rike cryai.la
vhtcl Dei,tcd .t rl8a. Lr saa chrdaLoordphically
Flre (benzen4chrororom) and differcnt fror z-s.It vas narked as Z-c.
'he cohpound z-,r v.! ch.racterize; aE rorr-
l, sorutlllitw tesr.rr yas sorubre in
n-h€xane spartnqry .olubleln6orubre in erhyl .cerate,
Benzenrchrorof orD, hot
in ord n-herane .nd
EthYI alcobal .nd
'o! functioNt group .nd n.P. see t.b)c I
_r)l_
2. Preparatioh or acetyr d€rivative of c@pound
Z:!tAn acetyl detivatrve ras prepa.€d2g and
rtystalrised rroh eth.nol \i,P. 1342,
The Inf!.red spectru of the 6eerate
delivative of z-a sh@ed absorprion ar 2940,1?52,1465,
l3?5,1250,1035, 97O anA 725 cF_l.1he Inrrarsspectr6 of c@pound z-a Ehoved absorbtion ar
3452,2q50, 1050, 14tO,t344,1062.1064,C?2rC6OrA4O and
305 cn _. Literatu.e 5urrey shored tbat Eliscdpound My be F -sitosteror hene Z-a vas cohpared
vith cn authenti. s.nple or P -sitosler.l { rhin
raye!, Infrared sp<tra, trixed berti.q poini),ltvas finltly corcludd rlEt cohpound z-a is identi.ars ith P -5j Losterot.
The c@pound z-q,a3 clhncterizd ns
1. Solubilitv te6t.c@pouD<r z-9 ras fornd to be readily soru-
blo in benzehe, chloroforn, hot n-hexane, sp.rlngrysoluble l. cold n-heene and iGolubre in erhyt-acetate, ethtl alcohd, and ,ate!,
tor functlonal gloup .nd M.P see table t.2, preparation of .ceiwl derivarive of cmbou^d z-9.
_94_
The quantity of z-9 eas i.6lfficient for the
preparation of deriv.tive.'fhe lnf.ared 6pet.on of coFpound z-9 .noted
absorption at 3Llo, 3430,tOIo,2960,2g40'zaqo'2a75'1670 |
t44A,t3AO,t37A,\22O,].21O,1135, lr45,tO3O,a40'?25 .nd
!'ra.lion 5 obtained on
ether eas concentrated anl finarly
E€d pressure to qive ! yetlovish
This product sas @rked as z-lo.
It vrs chalacterized a3 follovs'
1 SolubirLtv test.It ra6 leadiry soluble ln petroleu ether'
benzerer .arbontetrachlolide' insoluble in ethvt acetate'
ethlnol .nd @thanor' rr"'
For [email protected] gtoup and l't'P se table I'
The quntity or 7-lo vas insurfrcient for
erutlob vith p€trole6
dietilled undet r.d-oir at 22o9l6.s e.
corPound z-to shoted
el!tion vith petrorem
disCltled undet reduced
240816.5 M, rhis
the prepar.tlon of deriw.tiw.rhe lnfrared lpectrm of
.bsorptio. at 3O0O' 1610, l4?0, 13c0
Fractlo. 6 obtai.e<r o.
ethEf y.5 concentrated and tinatrtpresbure to give a yelto*lah oll at
prddEt Yas oErked as z-11.
lvatiE or cdpdnd Z_lO
_q5_
It taa characterlzed a. follda.
r. gg!!ji-L!!Ijc:g lt 'a6 rreelv sotuble in petroreun
ethe! t enzene, carbontetlachlolide, in66rubl€ in othyr
ac€t:te n-herane, acetoner eth.nol and neth.nol J :
For runctlon.I qroup and \.P see table I
ion or delivative ot cdThe qu.ntity of z-ll e!6 insufrlclent for
the preparation or deriv.irive
the Inftared Bpcctrux or cdpoubd z-ll sboved
absorptron at 3000,1610'14?O'13q0 c! -'' Fractlon ? obt.ined on elution vlth petrole_
M eth€r ras concentr.ted .nd finallv dist1116d lnder
r€duced pressure to 918 a verto{lsh oir ar 2403'/6'5 m'
fhis plodEt r.s trarked as z-I2.
!t vas crDrsctelize<l as foltous'
1. Solubirltv teat.It vas re.dlty soluble in pet'roleE etlcr'
carbontetrachloride, !n6oluble in eLrivr tcelaEe'
ac€tone, ethanol and @tranor .r ' t '
!'or fostioml qroup .nd M.P. see t.ble l'
2.
'r'h. quantltY oa z-12 ta. insufridi€nt for lhe
prcpafatlon of deriv.tivo.th. rntr.r.d z-12 shofed absorptton
e or .@ound ?:l?r
at IOOO,I rilO,l.ltr),1:JqO, ?50 rnd,?oc;-r.f(actioh 3 obtainad etutio. vith pe!
ether. lhe fractjon uas concentrated and finalrv
under rcduceS pr.ssur€ to qivE n yerrdish oil at
6.5 nn. rhis oroduct vas narked as Z-I3.
2042/
tt vas characlerizd a6 folloes.
1. Sorubi r irr te3L.
lr qas .aadiry soruble ih Det'ol€s ether'
benzene, cart'ontetra.hloride, insolut'le i. ethvr aceLate'
ne-hexafL, c.pt onc'Fth.nol dnd Eethano!'
for functjonal .lroup and r4.P.
2.
'rhe quanci!y of z-13 va6 insurficient lor the
preparation of derivative.Llrc lnlrared sP(ctrun of z-t3 sho'ed absolp-
Lion a! 2 ''',l'4C,l4 t''nrractio. I otlained on elution tith ben26ne'
shore., the presen.e of three conpounds (TIf I bente'r +
chro.ororn). rhis fr,.tion vas ewarorared Io drvness
and Left for rurtt'cr ihvestioations.
Fracti6n 2 obtajned on erution vith bcnzehe'
ehen arroved to .tand at roh temperature fo' tte'tv folr
hours, save a crysLalrine pioduct. Lt sas firEered aid
r*rt.r!r I rzod rhc c polhd Darked as z-7'
Pr€paration of driva!ive or cohDound z-13
,w
Ir va. cha.acterig€d .6 rollo{s.
t. :iorubil!tv test,rt s.s folod ro be readllv soluble in bentene,
chrorororE, itsoluble in ethyl acetate' n_hexane'acetone'
eLhyl al.ohcl, rethabol and *ate!.
For lunctional qroup and J P' 3e table I
2
An acetyl derlvative {as prepare'd29 and
rrrysLalrised froh eth:nol, x.P. 'r342'lhe Infrared spectrlr of the acelate dettvatrve
or 7-t sh@ed absorption at 3ooo'3loo,l5oo'l4oo cm-l'
1he lnfrated spectru of cdpound z-?
shosd absorption at 33oo,3ooo,laoo ,1450 ctr-l' 1195'72o
Fractioh 3 obtained on elution vith b€n4ne
{hen allryed to 6tand a! ro@ t4Pe'ature gave corou'ress
c!yst.f5 after .bout trenty four hours'
fhe solid @terial vas firtered and r€crysta-
1l lzed fr@ b-heene.
fhe [email protected] rarked a3 z_3q, relted 't ?r8'
It sas charlcterised as folrovs.
!ior or dcelvr derrE!rve of cdbound z-7'
ssl!Dil.r!-v-l-9s! .
)L was found to be raadlly rolubre in Detror-
eu ether, benzene, .hroroforr,insoluble rn acetone, n-hexane,
r'or functiohar qroup
2.
c.lbontetr.chro!ide.ethyr arcohol,h€thanol.
ahd !.P see table L
P!.barJLior or acetvl deri% r4e ql !sEp9!!!LZ=l:.
r4rystalr is.d fron etlEno!, lr.t.'lhe lnrrared spectrun
tive of z-34 sh@ed absorptioh atThe tnfrsred
at 3OOo, r4(0. r4oo,74o (w) cn_1,
= r34?,,
of the acatate deriva-
IOOO,l{5O - 60 ( s-s) cn_r
,-39 sho{ed absorpt io!
|raction I obLained on elltion tith chro.o-
of Lvo .onpounds ( 1Lr-- rchlororo(r+ elhyr acctate). this fra.tion va3 evaporated ro dryiesss
a.d left for rurtner invostinati.ns.L r.crion 2 ot'ta ih€d on erution rith chlorofo-
rn vhen loft fo. t{enry four
cryltars. 1he sorid product vas firteredand rectyslallized fron beizene. the conpound n.rked as
iL rds.harccLefrsed a5 (orrors.
I. sol obr !t!t_lge! .
\n acetyr deriv,Lrve ra6 prepared?q and
It vaB found to be readiry sorubre in n-hexane,
99-
benzene,chloroform, vas insoluble !n pctrorem ."thot,
acctate, ethyr alcot!6l and raLer.
for functionar group and v.P.see t.bre r-
2, !!9p3I4L&ILELZ | 4 dinitloFh.nvl hYdrazjne derivutiYe
\ 2:a diritropheny htdrazone vas DreDared and
r4rysta)r1spd rrdh eLhanor r.:. 12Oi.
rhe Inffared spe.trun of the 2:4 dinrtr.phc.vl
lryd.ozono sl)or.d the abso.r!ior tt llOO,16110,800,775 cr_r'lhe rnfrar.d 7-l .onpdund shovod absorrtioa
ar 3050, looo, L?5o, 1r,4o, 150o, 1450,720 (v) cm_r.
:raction I obtai..d on eluli4n xirh .hl.roaor.or t'o couDounds, it vas tharefo.e
ne.,cssrry Lo sotera!€ Lheh. lt {as obs.rve.l
conclhtrated soluLioir or Ll,is fraction
srand overniohr., a crystalline product vas
{as riltpr.d, rrr.aredry va6hcd lith.hloroforn and
r4rysta1Iiz.:d f.d .hlororo.fr . This .rystarrine rrodEtvas round !o chronaroqraphi..lty lberzene - chroroaorh)
Inarked as z-4 (:r.P = 70:).'lhe holher riquor
alter lhe reDovnl of z-4 and lha qashjhcFtere conbtnod
and concen!rdt"d. rhin raycr chrmtoqrnphy or this.on.6htr.te shoved rhe pre.enco of one frajor c6ponen!
*irh oths. nino! thpuritt€.. rr Gs rherefore slbj<red
-IOO-
to .orutrn .hronatoqtaphy { si I i.a-qe1 ) us inq .hrorcf dr
as eruant. lhe fraccions.o.taininq the na)ot conponenr
,er€ rixad. .oncentrated and leal for crvstarrsatron ar
Irler about hours a {hil.
product .rysLallized out vhich tas filtered, tashed xith
.hrorofoln and recrystalllzed fror the satrLe sorvent.
Il {as rouhd to be readily solubl€ ih n-hcxane,
petrores ether, benzebe, chloroforn sFarthqlv sorubre
in acetone and insorubre in .'thyr acetatc, ctlryl .rcohol,
hethanor and {ater.
Ir vas found to be difrerert tt6 t-4 l'twchloroforn) and vas erked a5 z-5.
It ras characterized as follors.
l. sorubi!irv tosr.
dr fr1.r roaal cr.up .nd .r,or of derivaLive or 7-4
u.oa incrusion cfiplex or z-4 x.5 prepared
Dathod and rkrtst.lrised froh n-buta.ol
, I 12- att ,
'lhd conpound z-5 uas characterrsd
tel-$r..1iq--gE!=It {as found !o be readirY solubte in petro-
!€th ether, bonzcne, chlorofcrn, sparinqty soruble in
acetone and insoiubre in ethyr acetate, etliyr alcolEl
-tol-rthanol and rater,
l12 -
Fo. furction.t g.oup and n.P. see t.ble I
!!sE!E9.9!--s!l|e!jr4*iE-.9!-4!A ure. irctEion cdplex of z-5 ya3 preprred
u6ul rerhod .nd lelyll.lliad frd n-butanol n.P
1343.
Fractlon 4 obr.Ined on erftion vith .hrololo-6
't€n all@d to crFr.lli.e .t 1060 terper.tule q.ve
colou.te3s nedle like cry.t.IE aator .bo!t lventy four
iours. lt ,aB flltered .id th€ prodEt rla r4lyst.tllzdflotr n-bexarce. rhe cdDound rarked .a 2-36, Derted at
r52t,
It r.a charrcr€razod as fotlora,!. solublrirv tear.
lt r.s re.dily aotuble in p6trole6 eth.rn-hex.ne spariNly solubre in .c.to.€ .rd imolYble inethyl, .c.t.ter ethyl, alcohal, reth.nol .nd v.te!.
For funccton.l qroup .nd -r.P ae t.bl€ t2. Preuration oa deriv.tive or [email protected] 2-36,
'r'he qu.nity oa tt-3.t vas ln.u..icient for rhc
plep.ratlon of deiivatiE.'rhe In(rared apectre of conpound 2-36 3h@ed
.bsorptloh at 3loo, 3ooo, 2OOO, t350, l5OO,rolo-4o cn_l. rhrfr.ctlons obt.ined oh.turio. vlrh ?rhyt acerare yere
Iefr ?o. fuither invesriqattof,s.
'lho benzene exrr.cr (Iar4.4 gh) of the pra.rstorj las dissorved i. minirum quahtity of b.r.ze.e dlld
adso.b.d on sitica-qer. rt ras iirst errrcd
rirh p€troreu ether (B.P . 60-;JoJ folloved by benzenc.
chloroforh aid ethyr acetare respectively. rracrtons oa
25O nt each vere colr4ted. Uach a.acri6r ras subjeri:dto thin rayor chrohat@raphy cbd sihir:r fractions ve..
varrous fraction6 vhich vere finatty obrai.pd
th dirferon! qiv." in labre 18.
l{)4-
I r.ction I obtai.ed on elutio. *ith Petrola@
etbe! vhen allded to cryslallise rt rod lelperature
gaw colourlesg cry.tals aftet abolt trstv four hours.
lhis prodrt yas Darked as z-l4 It eas rirtered .nd
.<ry6talliz€d frff bentene. The cdpound rlt€d at
7o-so:.
It vas char.cterizod.. ?ollor3.
r. s9!$j!!lx-l€s!.It s.s round to b€ le-adily aolubte ln petro-
leu ether, benzener chlorofort .nd c.rbontett.chlorlde,
and insoluble ln .cetone, ethYl acetrt€' 4th.nol .
ror ruEtion.I .lroup i'P. s6e table I.
2.
An acelyr <lerivative ras prep.rd2g lnd
rerystarlised froD ethlnor i.P. 1348.
The Infr.r€d.pet.utr of ihe acet.te de.l_
vat ive of 2-14 Bhoed .bsorption at 3300'3100'1650'l4qo!
l4oo, aOO,t?5 -_1. Ite so*tt* oa cdDound z-14
shde<l ahsorpt ion at 3100,?noo. lo?5, la00' l74o' 148o,
frrctlon 2 obt. ined on elution Yith petroleu
erhei. 'r'he alaction vr! cofe.tr.ted and finalry didjrl-ed undEr rerdEed pressu.e to qive a yetlorish oir .l2$2^,,3 tu, This prodet r.. D.rked a3 z-le.
ara!ion or .c.'tvl derivhtiv. or cdpound z_
-105_
It las characterized.s folloYs.
L Solubilitv test.rt ras fou.d to be readllv solut{e in petroleu
ether, benzener carbontetr.chloride' insoluble in chlolo-
forn, acetone, h-hexanc, ethvr acetate, €thvr arcotal,
netlEnol a.d rate..lor functionll gloup and 8.P 6e table I.
2. Piebarat.ion of derivativE ol conpound 2-16.
The qu.tity o? c@pound 2_16 ta6 insufflclent
for tlp preparation of derivatrve.
'rhe I.frarcd 3p4tr6 of cdpound 2-16 ah@€d
absorption at looo,Ihl2,l4lro,tlgo cn -.
lraction I obt.ined on e)uti6 vilb benzene
vhen arroEd to stand at
t{onty four hours qave .orourless crvstars. It vas
filleled and rec.ystal!ised ftoh n_hexane lhe.ohpoun<l
narked a6 z-ls, h€rted at l5og,
rt vas characteriaed as forl@s.
1. Solub) Litv test.rt 'ac found to t€ rcadily solubre ia benzene
chrorofortr, carbon disulDhid." hot h-hexa.e, and sparing_
ly soruble in cold n-hexanc and insoluble in ethvl
acerate, ethyr atconar, uater, hydrchloric acid and
:odts hydroilde 3oru! lon.
-l06-tror fufrio..t qroup and M,P. 6ee t.bte l.
2.tPreparation oJ .lerivatic of cdpoud z-15.
An aceEyl derivative vas prepared_-and iec!v6_
rarllsed froh elhabo1 M.p. - ll4tfhe Infrared spectrur of the acetate derivative
or z-15 sh@ed .bsorption at 3325'3loo,2lO0,l360.l5lO'
tO5O ctr-I, The rnrrared 3p4tr6 or copound z-15 si@ed
ab6orption at 35oo,3ooo,la,3or l5oo' I3co cm_l.
'Ihe fractions obtai.ed on erution {ith benzene,
chlorofor6 and ethyl acet.te vele teft for furthe.
!e9!.9!9-.9r!.Iie! .
llc a.etore extract(199.3 g) of the Plant st6
sas dissolved in riniid quanttt! of acetone and .d6orbed
on a colunn of sirica-q€I. It ea6 fir6t €luted ,ith
peuoleun ether (B,P 6O-803i foll4ed bv benzenF, chloto-
fom and ethyl acetate relP€iively'Fraction6 of 25o nl
each {ere cotlected. Each fra.tior vas subjeted to tr,in
r.yer chroraioqraphy and slsllar fractiohs Ero hired
vario!3 fractlon3 rhich rele finatrv obt.ined
in differ.'nt oluants ar€ qlven in table 19.
lAllL|j !|\
t2)II (T)
rrr I r)
tv (r) I -5
ra.tion I obt.i€d on etution virb pet.olcMthe presence of rro c@pounds (rl.rchtoro-
IacFlare). lhtB fracLion vas evaDorared tulert ror fulther inresriqations.
r raction 2 obraired on eruriob rith petrotesether rlFn atrmd to cryst.ttise at !o@ tehper.rure.Shjninq cry6tars €re obt.ined afrer about t€nty four
filrered and reciysr.rrised fror benr€ne,'lhe conpound !'a!ked as z-1?, nerted ar Boe.
It vas fdund to be readily 6orubr€ inbehzene, chlorofo.tr, carbon ter.achro. ide
and in6olubre in acetone. n-hex.ne, ethyr aceratc,trerhanotand ethyt arcohrr.
Ir ,as characiert6ed as folroes.solubil ite test.
tar furction.! orouF and .1.p 6ee
2, Prep.rarjor of deriltLiE of coroound z_t
A 2:4 dinitroDtEnyt hydr.zone Esdrd .c.rysLaltis.d rr@ erhanor .i.p. = l2o:o
'r'l€ Infr.red sp€ctru or rhe 214 dinitrophe.yr6hoved absorpt ion at ltOO, 1680, 1490, l4OO, tOO,
lie lnfrared specrlu of coopound z-t? 6hov6d
at 3ooo, 1a50,1480, l3ao cn_l.
frr€ t.actions ob..ired on erution {t!h !.nzener
-109-
chroroforn ahd athyt aetatc Erc refr for aurrher
4ts9!tl-e!!4as! .
'l hin tayer chretoq.aphy of tt€ vlllocflactions rr@ arcohdic oxtlact sho€d tlc presence
of . cmplex lirtute of c@pounds. They €ro not vorted
out and nec\d fxrther inv*tldntior,(b). l,rtraction of relve.
rhc extla.tion vrs perfor@d in differenrlhe rollovinq orde..
(i). qtraction riLh oet.oreur .'ther.
^ir dried Fra.t @tarial (teaves 5,1r8 kq) r.3
cut into $,!arr pi€ces .nd .errux€d rirh pelrores erher(L.P r0-q0a) ror abour tro hou.s. lt vas filteled .rdthe residue r.s kept ror extractio. rirh benzene {des-..tbed lntor), llre cxtracr {as concen*atod and finallyevrporateri. 'r'he dark oreen extracr rhua-obt.ined nsnahed .s pL'rrorea ether extract.(ii). Dxtraction eitb benzohe.
1he rosidu€, .frer extruction vilh petroremet.her, vas refrux vith coMerciar benzene ro! abour rhroehours and iL ra3 filterad ard tlE reslda v.s kept forertraction eiLI acetone (de.c.ib€d r.rer).1hi6 ertr,cr
.hd ltn.rry evaporatd, 1he grenish
-l ro-
trr:s ohrn ib..l
ih{r rrsidLri arlor {'xrracrion virlL rjenzer.r,
wirt.romner.idt
vds rirr.'red antr tho residuc vas kcpt for exr.a.tion viLh
'rLhyr arcolidr (d.-scribed tdr.cr). lh,-. eatract.vaporar.d. Lrr. dark biorn seni sorid
rrs nan.rd accl onc .rtr..t.(iv). Lx!rd.Li.n vith ?rLhvt rrco!i61.
!h. r.isjdF, .fLr'. |xtra.ti.n rith acetonc
rjth conncrciat .thyl .rcolor for rhre?
'ill.cred ald rosid,tr u.s ro!ained iorLrn. nL.ohar .xrra.r ras
d.rn f inar ry {r!ap.rnr..i,i,d n\ ,L.r. :ll,..rr.
-113-
rract ion I obt.ined oh elutioh vith petro-
1eu etlc! sh€n alloved to crys*rrise at rom tetrp€r-
ature qavc corourress clyst.ts after about tE.ty fou!
hou.s. tL 'as rirtered ahd recrystalrized ftob n-teaane.
fhe c@pound harked z-ls, nerred at 554.
It vas cbcracterised
I . !p]$i-Igr-19€! .
rt vas found to be readity soluble in petrolc6
ether, benzene, hot n-hexane, hot chro.oforn :nd insolu-
blc in cold n-hexane, acetore, etbyl alcottltl
For functiohal group and fl.P aee tabte I.
2. Preoaration ol derivative of co[oound z-lq.
.\n acetyl derivative vas pretared2qand reclv-
srarrised .roh elrunol n.P. rr€.rh.! Infrarad the acetate de.ivative
ol z-19 shored abso.ption a! 3OOO,l49O,l3q5 cb-t. the
lnf.ared spe.tru or cohpound z-l') shoFed absorption at
l3oo.ll50,2o5o, IrJ75, Ii,00.t53o,lo4o c!Fraction 2 obtai.ed on elltion vtth p€tlo].uh
other vhcn alroved to srystal,Iiso at rom teDp€rature
gave colourrcss cryslats after about tEnty four hour6.
l! Eas fillered and rec.ystalrised fr6 pet.ore6 ether
(!j.P. 4o-6oe). 'r'he .onpound marked aa z-3r! r€rted at
66?.
It ras charact€rized as folrds.
for funcrionar group and u.P see table r.2, Prepa.aLion or derivariv€ of conpou.d z-l?.
an acetyl deriv.tive vas prepa.edzg an<l
recrystalrised froh eihahor r'1.r' 1343,
fhe lnfrared spectrun of the acetate derivativeof 7-3t shoqed absorpt ion ar 3350,1525 cr-}.l he Inrrared
conpound z-37 shovcd nbsorption at l5O0,3l0Or
3OOOr la5O, I775,15OO, lOlo m'r.
l. Solubtlitv test,It vas found to b€ (eadily soluble in perrol-
h-hoxane, hot chloroform ahd ihsoluble
rn acetone! eLhyr arcohol ah.r rethanor,
f'raction I obtaihed on erutiob vith petroleun
ethof rheh alloyed to stand at roon tmperature for Lventy
four hours gave corourress crystals. It 'as flltered and
recrystarrised froh petrores erher (B.P 40-602).1.he
cohpound nalked as z-3s, netted aL 603.
-l!4-
rt ras char5ct€rized .s forlovs.
It 'as found ro be .eadiry sorubte in petroleun
€lher, b€nzene, chr o.ofoo, c..bontetrachlor ide, inso I ub rc
in acetone, ethylacetate, ethyt atcohDr, trethanor ahd
ior functional qroug and 11.P see tabre I.
-1ls-2. Pr6aration or deriv.ti€ of cdpound Z-34.
An acetyr de!rvatrve *a6 prepaied2gand
r6rystarrised fr@ ethanor x.P. r34?.
'rhe rnrrared spectrM the acetale derivative
of z-3a sh@od absorptlon ai 3!5o _ Jooo, tneo,t4oo *_l'
The Infrared specttu of cdpound z-34 shoFd ab6olptlon
at 3O5O'l?a5,l4co,14OO,?2O {e) @-r.
the rest of !l€ t.actions obtained on €lution
vilh petrore@ 6thet vere left for further inve6tiqations
Fraction I obtai.ed an elltion vith t*Eene
{hen arlored to crvstallise at rod tetrporatule gEE
shinilq crystars after about tventv four houts rt vas
firtered .nd re.ryslallised from petroieuh ether
(B.P 4o-oo2). T he cdpound s..ked as z-ltl' herted at
It eas chatacterlzed as fouo,a'
l. solubiltiv test.Lt ras folnd to be readily solubte in petrolew
€therr benzene, n-h€xaner carbontetrachroride' tnsolut'le
in .ceione, .thyr acetale, ethyl alcoh.r' lethanot
F_or functlonal qroup and n.P 6ee table
2. I!e@$-s!--9!-9e!i!si&.A urea inclusio. conplex of z-la ras pr€pared
by the cual netlEnol and reclvstallleed frd n-butanol
x. n. ( 132-r43),
-ltfl-
lhe lnfrared spettun of ure. cdprex of z-13
shoxed absorpLion at 3lOO,1400,l4OO cn -'The rnfrared
spectru of cohpound z-Is sho{ed absorption at 3ooorl5o0l
rlaction 2 obtained 3s on elution tith benzene
sho'ed the presence of four corpounds. 1t'ese four c@pounds
rere seDerated by Lhin rater chronatoqraphv (ben,ehe )'
'fhese products rere harked .s z-2r ,z '21t2-22 ;Z-23 ' r^
order of decreasi.q cotrpouDds hoveEr
have not yo! been clFracte.ized.
Ibe fractions obgain.d on elution rttli
chloroforh, ethyr acetate vcre rert for investiqations'
eatrrct (25 sn$) of the plant
reaves vas dissorved in ninihm quntity of benzete and
adsorbed on a cotun 6f silica-qer. It vas first eluted
rith petlorem ethor (B.P 60-80g) folroted bv benzehe,
cbloroform ahd ethyl acetate respectivelv. Fr€ctiohs of
25O 11 oa.h {ere correcEed . [ach fraction va6 6ubjected
to thin layer clrrohatograpby and sinilat fractions rere
va!ious fractions rhic|l vere linallv obtained
i. dirrcroot qiven in tne table 2l'
.r. . rn ' :o', . . ,1 n., o \Jnba! or scol5ctr',r ioa ia n,^', 'rd;'-. ion
I. ( r) r-i, I,ctrorelr r iqhL yelro{ r'hree spors
(2) ?-l,r) P.-tror.w Liqhr yerros :iinq1!r sDoL
l3) ll-lr) PetroreM Ljdht yerlo' sin.ile spot
rr, (l) l-l(2) 4-r Udrk y.rrov
lrl (1) l-? r'lrroroaorr l.i<t)rr qro.n
(2) l-0 chloloaor! riqht qieen
rv. ( l) 1-4 lthyf
-lln-
Fraction 1 obtained on Glrtion rith petroleun
ether slreed the presenc€ of three spots (TLcj chroro-
forn + ethyr .cetate).'Ihisto dryness and r€at for rurlhar investigations,
1t "as
chalacteri6ed a6 rollors.1. !91!4.IL!_!9E!:
It vas aound to l,e rendlly soluble in petrolew
ethe. lFnzene, .hro.ofo
!-ract.ion r obrained on elution ,irh parloroueth€! rben alloved to clystallise at r@n tehperature
.oloultess crystals vere obt.ined aft€r atout tventy foUr
filtered and recystarlised troh ben2ene.Tlre
cdoourd harked as z-4l,@rred ar 6?3,
It eas characte.lzed as foll@6,1. Sorubiritv rest,
It v!6 found to be .€adily solubre i. petroreuether, benzene, chtorofoft, carbontetrachloride, hot h-
hexane, spari.nqry 5o1ub1e ln hot acetone, insofubl€ in
eLhyI ccetar., hethanol and eLhyl dr.oh.!,tor functionar
2. Prebaration or dcrivatlve or conpound z-41.
^n aceryr derrvarrve qas prepared2g and recrys-
tallised rrd orhanor tr.P. 134€.,
llre lhfrared sp€ctrun of the acetate derivativeof Z-41 shoFd absorption a! 3OOo,l43O,I39O ch-r. rhe Inrra-
red spectrun of cohpound z-41 slored absorption at 3000,
Itrl5,(s), t?ro(s),r49o,ll9o cn_r,
obtained o. elution rlth benzene,
.lrlorolorm, cthyr acetarc rere refL ror investiqalions.Acotono and arcohar exLrats,
abd arcolol extracts have nol yet
been investiqsLed.
-120-
c. q!!e9!i.e!--9!-!:9!sr.9:Air dried fr.over. of the plant (5ls gns) eer6
cut into piees and refruxed tllh petloleu ethe! lB'P'
60-80:) fo. atrout thlee hours. rt tas firtered. concent_
rated and finalry evapor.ted !o a dark qteeD svrup' 1hi5
vaa nalsd as 'etroles €ther extraci.
rton a'd isoration of the constilupnls ot
exLracr of rhe flover.lhe petrores ether extract (I4 2 q[s) of
tho plant rroters uas <tisEolved in ninin@ quanitv of
benzene and adsorbed on a col6n of sirica-qer' It vas
firsr cr,uted yith petioreu etbe. (B'P bo-sob foLrovcd
by benzene, chroroforn and ethvl acetatc resperivelv'
liractions oa 250 hr ea.li {ere .oll€cted' tach ft'ction
e.s subjected to thin raver ch.osatoqraphv and slhirar
f.actions ter. iixed toqeth€r'
various f.actions th iclr tere linallv obtaihed
in different giEn in tabre 22'
'!-i !-r:--:.--I1ll-I
lil-i--liir r.,. u.'r", ,
"*t',- ' solurion tn 4a']x t'a'tr-
l, ( r) r-l jlix snots
l?\ 4-t) retrorcun Liahi vcrloYelhar
lt. (r) l-r LiqhL Ycrl@
fII. {l) 1-l Itlry} l,iqht 'lreen ruo spots
12) 4-. r-Lhyr l,iqlrr qreen fto spots
-L22-
r'ra.tion I obtnincd on erution sith perroleun
erhe. showcd Lho presence of sjx spots (Tlx, pelrol.un
ether r benzene ). rhis fraction
drybess and lert for fulthef, investiqatld.s.
fraction 2 obaalned on elutioh fith petroleu
ether rhen all@€d to cryet.rlise at roon tebperature qaw
sbining c.ystals after Ebout trentY rour houls. rt tas
filtered and recrystallis€d fim tenzene. fhe cohpound
larked as z-2s metted at 7se,
.r uds .rcracterr2nd
L Sorubilitv test,to be rcadiiv solubr. petroleur
ether, bcnzcne, chrorofortr, insoruble in
cord n-hcxane, ethyl ac€tate, ethvr arcobol and retharcl
or rLnctiohal qrouP and r'P. se. table t
2,
r\ 2t4 dinitrophenyl hydrazone {:s
reclystarrised frd ethanor r,P. rro3.
'rh.. Infrared spetrs of tha 2:4 dinit.ophenvr-
hydrazone shofed absorption a! ll0o,l650,I5oo'l40o,noo'
?30 cn_I, Iho rnrrared spe.lrun or cmpolnd Z-23 strotod
absorption at 3OOO,1?5Orl5OO,14lo - 6{),?2O (t) cn-r,
Fracti6n r obtainod, oh erutjoh vlth lren'ene,
shded the preserce or roui cdpouhds.'rho separrtion or
araLion or de.ivative !! !91!!9!!d-z:?
-!23-
Lhesa cdpounds calried out by Pr.pa.ative thin lavcr
chro@tosraphy (chrorof ort). f_our cdpounds100-""
and harked as z-24, z-25, l-26' t-27 respecL\verv ' \n
order of decr.asinq Rf value.
'fhese cohpounds *ete then characterized as
aharacteri2ation or connound Z-2n.
r. 99.Lcbi-L!!v-!9E!.r! ras found to be leadirv solubro in petrolew
ethe!, t'enzone, chloloforb, n_hexane, sparingrv soruble rn
acetone, and insoluble in ethvr acetater etnvl alcol€ir'
tethanol and raler., or runctional qroup .hd It.P
2. Prepara!ion of de.ivative.A urea incrusion conplex oa z-24 ?as prepnled
by the usual nethod and recystarrised frod n-butanol l1 l)
( 112-34e) .
ll1. rnrrarFd sp4trun or urea 'onblex of z_24
shoeed absorption at lToo_350o, lo00'1650-60'1490' 1390
ch-1, The Infrared sPectlm of cmpound z-24 shoted
absorption .t looo, l4go,13?5_lro ct _.
Cha.acterization of conpound Z-25.
I. solubilitv Lest,
It ras round to be teadilv soluble in petroleuh
ether, benzene, chrorofotm, n-hexane' sparinqlv soluble
2. Ecp3!e!ieLel--gc4J3!ije-a urea incrusion conprer of z-25 {as prepdrod
by the usual 'etlrod and lec.vstallised fr6f n-but'nor
:1.P. (r32 - 34?1.
Ihe Infrared spectrfi of urea c@plex of z_25
shored absotption at 3100,155O,I500'1490'110O,1050,3?5,
aoo, 775 .n-1. rhe tnflared spectrum of conpound 2-25
shoved absorption at 2950,I{5O,llso ch-1
CharacLer izat ion or .6eoound Z-24,'
r, solubil itY test,
in acetone nnd insolubra in elhyr aceiate, ethvl alcoh.r
l or fun.Lional qroup and
for funccionar qroup and n.P. see table I
PtcDarntion of ur.a incrrs j orl
rhF quan!ity or z-2 t' eas ihsulf iciont ror th4
preparation ol derivative.
characlerization br cohbound z-2?.
l. solubility rest.
to be .eadilv solubr€ ih Petroleun
ether, benzene, chrorofotft, n-hexan€, spa!inqlv soruble
in aceeo.e .nd insoluble in ethyl acetater ethvt arcohOr
IL vas found to be readlly
ether, bonz€nc, chrorof oln, n-hoxane,
solutJle in petroree
sparindry sorrbre
-12t'.xtractton of alkaroids.
rhc residue 1e!t afler !h. €xrracrion of
the plant nateriars (sts, r€av.8) vith organi. 5o1ve.ts,
{as used fo! the extraction of atkaloids as follor6.seperatort treated
f,ith ln hydrochroric a.id and left overnight at r'Mtelperatu.e. lhe extlact vas filtered and nadc arkarrne(amoniaJ. r'h€ hcutral eltrac! ras extracted rith chloro-
forn. Thc clrroroform rayer {a6 ccoarated dlied over an-
hydrous sodiuh sulFhate and evaporated to dryness. The
q|ffy ruas thls obtain€d eas tab.rled as extr..t A.
'ltie aqueous rayer ras saturated uith comon
sart a.d extracted rith chroroforF. This ertrict ra6
firtered, dricd and evaporated ro dryness.'Ihis vas l.belred
lhe extractiob and isolation of alknolds ftoftdiffelent parts of the plant have been stu.(ized in the
rrov sheet diaqrah ob paqe 127 .
iodividu.rry rested for rhe preseh.e of alkaloid lry
spe.ific alkaroidar .eaqenrs, A s{nnary of tne6e testa
i3 qiven in tablo 24.
d
n
Fl !ia
f;
I
-lzt -
I'
E
t
jii
i
1.
f,'?
i
sl
iltl,fl
rq1t
1f,
frl
:l
If,
in €xtra.L a nnd-Ll
r.6 the steF.
Dxtracts a aDd B on (llrc: chloroforr +
ethYl acetate) shded the ptes€nc€ of lhr€ identlcar
cdpouids. ihe serp hpnce 'dt'ined' rhe
seperation of tbe constituents of the c@bined extrac!
sa6 finallv achieved by preparaLive lhin lavet chto-
natoq.aphv (chrorofolb + ethvlracctate) The three
/ lq rn ordcr o'Products *ere
decr€asinlr Rf varue lhese cdrpounds {ere then charac-
It sas found to be tFndilv 3olubre in
, meth.nol and €thanol and insorubre in
eLher, benzene'
for lunctional qroup a'd M P see table l
The rnrrared spEctrun of corpound z_33 shoved
charactPI zarron or cdDound r_:14
r. sor!tsi]ilflegli
absorpt ion at 1650, looo, Ilr5o' l49o' 14oo ( s) ci-r'
rt ras found to bc f'adjlY so1
ethanol and insotuble
b.nz.ne, acetone, n-hexane'
te(ized as folrdscha(acterlz!!&!--g!I. soluhr I iLv LesL.
ror run.Lional qroup dnd rll'.
'lhe Infra.ed spectrum or c@pound z_34 sh.rxed
absorption at 29aO,l?lo't460,134o (s) m-1.
characterization of cdDound z-15.
l. sorubirtv res!,It sas foDnd to be freely soruble in clrloro-
fo!h, Dethanol :nd ethlbol .nd insorubre in pteroleun
ether, benzene, .hlorof orn,
16r functiohal qroup and x,F see lable I.1ne rnrrared 6p4tru ol cohpound z-3o sh@ed
absorption at 3lo0.lrroo {v} m -.
tsoration or tne arkaroidg brcsr)nt ih Extract n and B
Lxtract A and r, on (lrcr benzene + chroroforn)I:l
sh@ed the presence of four idehticar cmpounds The
rere hence conbinod, rhe seperatron of th.
con6tjluents of tne combired finally achieved
by prepa.ative thin laycr chromrtoqraphy (benzene+ chloro-
rorh). rcur products vere sepetated they
as a-2c,2-1o,2-31,2-32. In order or decreasinq Ff varu..
These cdpounds sere then char.cterized.s folld6.chara.ter r2a!i9!_!Ilcpound 7-2..
l. solubir itv test.
-lrl-
rL r.s lound to b.,rc.rdirt sotutl': if chrn.o-
fortr, nethahor .nd ethanol a.d in3oluble in petroreuE
erher, benzene, aceton., n-hexane.
o. runctionar group and It.P. see t.bte l.fhe r.r.ared spetrun of cdpound z_2! sho{ed
ab3orption a! 3050, l??5, r5Oo, l4oo, ro30 cb_1.
ch.!.cterization or c!6iaud /.lq.1. So.Lubititv test.
rt eas folnd to be leadilv solubre in chloro-
forn, nethanol and ethanol .nd insorubra in petroleu
ether, b€nze.e, acelone,.-hexane.. !,,, r' \.
ror runctional qroup and Y'P. 6ee table r.'lhe lnr.a.ed sp.ctrm of cdFound Z_]0 shd'd
absorpt ion at 35oo, l2oo, 2orJo, laoo, lloo, lo50 ch-1.
q.be4s!edzE!.!9!--9!-s!sE9$g-zil.
1. !.9.!!j-l_&t-le.!-LIt cas found to be readity soluble in chlorofora
nethanol and ethanol and in6olublc i. petroleua ether
banzenc, a.olona, n-hexanc.
!or func!ional qroup ahd Y.P
'lhe Inrrared spectru or conpound z-31 sh@ed
absorption at 3050,l2ooo,ts50,I5oo'1250,1040,765 (t) ch_r'
characrer izat ion oa cmpound 7-12.
1 . 9e!-!bi-!i-!L!SS!.rt ras found to tre readiry solubre in chlorofonnr
-13l-
,9€ .iE€: ig.d i:'l !i:i !*s!-1:'. -Bs" a rEil i *il-i ;i6" 3-Bl;iB $".:"a! fli i-a! Fi'i F *l: +Egiil$ glelE E;!i! liEr! iiIsE;j;.Et e44I: P:-66 i6i6! i6!o!
iErie,i!tsll 'iiii!;;aIe ;'"r: g
t
;. " ,,!
!i! ;:X6.s n!
E
3
q6
tltlEIslsl:l3l
i6, I
i! I
in
!!.
&:
6o
F'
B
-134-
s1 .".9 .s! 5i 's:r.!g 9;r s3: i.bs "-i 9i r:: ii: -Aa: " r;-cY:l :ra.:3i. $;j! fi;d.t!:: ;g:qEb:! r i;: g;ae
:tiB: ;ii$;*iF ;EgB FEi;
:,Eitii*iEiEl
i
gJ 63
-!15-
6
9E 563i
> > ., b 9!6" ; 6.. o 6i,:aie rFii rtla ;i*.i89 B,:ff ff,"i .dF.:." o:.o o:9' "!rts# *ala fr;? $;
L
cL! 9
lres.arch raboratories of ttte cheri3try of
xatural Produ.ts, rnstitute of chemistrv, univerEltv
of sjnd, ude! took a ploj€c€ to utilize the haturar
resources .nd .6peiallv the pranL resource6 of this
coun!!y. A nub€t of plant6' ehich ha@ apparently no
use, gro, abundantrv in ou! countrv' Besides' 3oF
herbs and shilr shrubs vtrlch lre bei.q aed tn crude
forn locally stnce centuties (or cu!inq various dir-
eases also {attanted €xPlotLatio. and throlqh inaesti-
unaortttratelv a 6ysten.tic
su(vey of the e.onmic vatue of n6t of tb6 t'!s not
been carried scientific arounds rt s'6
therefore thought nece€3ary to conduct a res€arch on
rhp '.drqorous
plahts of Pakisran.
Pro6opl6 glatrdulosa rs a p'rc
rhe rJrant baterlar sas extracted vlth petro_
res ethe!, benzene, cblofofor!' ethvr acetate an"
etha.ol respectivery to facjliate the isdlatioh or
various co ponents. Tl-c a.d columh chroratooraPnic t4_
hniqle s.re used to obtain the cdDounds ih pure fotr'
In arL, forlyDha cdDounds eere rsor.red 'rot nrosoDis
B
! r.i L t j I_t!ilrur. ';. i, a., l^it, vor,f_l
2.
3.
. ari. u.dr4d Druorndid",..r. FirFfauar. ).?o, D_i.F.:\. .hcpra, T!., a j,)pra, .,r,, ,t..da"Crob.a s i.di.r..ou6 dru(s or rndl.".u. r. DrLr and .;ons, prtvat€ rihjrcd.b]-2. ihid F-111.
c, ,t. Yultar, l.t. s.hirrla..1nd ...r.tc5r, I, j3n.
lO, P. E. roodsoar.A. s.tnoiderr {r?auqolfi.n I ittre
5. r. nonald, nsy.therjc Druqsn, p _ 268.
6. ___ , jrrir. :iearr.r.. re46, ! ,r.rr.?. R,J. vakir, jrrjr. ,eart ,r.r tr4qr l! , l5o,a. s. Sjddiqui nnd r.s. siddiqui, J. Indt.n. ch€r.
puhr js\ers. \es Yor*. r,t.
s6, lrr.,, f? , ]r, ihi,r 1.r,, ! . 514.
rrosron, ,ras$.\eu,, I r57.10/.). R.n. oo<teord. I.r. rradar, ,lrj.ket,
and u.w. iersre'lt, rour, Atr. .\en..c.2O?3. ibj.1 ).57,
at ek, .r.r er/ naccn) I
. 12- ,ranan, J,t:rn. :red., la4r,
,ldnkin and
I'
, tq56,l!,
t4! r
?.Q,60.
dlus,. rarular London, 1'r,15, 15!,..630.
t42-
F.\. ChdDra, 1.., cronra, ,i.t_. ,rahda-choprars indigenous dru.s of rndia"!11.
Dr"' ".0 sons, privare lihted,
rt. I;): !il.:, .(.r,. . a-da And f.D, c.pu.,uropra.s 'rdi(erou, druos of rhdja,., ie.o"d ediiro;,3:i;.""" '"" I inited' carcutt'' ra5n'
13.
22.
lar E.E. Trrner and r,.lonqans, qreen and
:larrls, "orqant. cheolst!r..,co, \ee Yor*, ri.Y, 1952.
1.. P. .r.er, " oro..i. ..er tetry" thiTd Erdlt.! editton,Ersevrer oubt is5t-c yol'<, !.y. 1q47.p-to.
zO. L.F. . leser dnd \t. r tesFr, "Sreroldr-, petrord.\er (orkr .Y. ta4t.
21, r. Dobriner, [. '{atzelt€nboden ard R.\. !:ro.e3,lIR absorptirh specrra or sterold - An trr!3".'.iley, Inter science, Nee rork, r-,y,,19i3.
or $,tR sp€crroscopy inDay, DiC, Londonr l96rj.
?3. J.r_. Sh@tery .nd n.T. Roserrs Jour. An.che6. !oc.!958, gg , 5121,
{. trelmnh, -lass sp4trGcopyi, olqanlc chdlcal!ppltcatlons. rc rad lritl rool .6p.ny, r'..r \e,York, . y, I.62| F-140.
25. ':. Fudziklevidz, c.D je.assl and u.w. $ltltars!"structu.e eructdatlor of \aturat Droducrs by .{as.q5*trometry , vol. l_! . olde- - Ddy, I\.., Londoh,1.64.
and D.it. fll1rl.!s, "ADDIic.rion.orqa.ic chdlstrtnr nolden-
!Q,1r,2r.. ,. ,.hian, .lr. L enbest, i|.0. €k and6ur. Ah. chea. Eoc., laa\, ?4O2.
-141_
2Ar a.r,J. nenlrey, "rrucidation of strlcturea hya^d atFii.al rerh^dsi T-.hri.lLF rf or4rri.vDr lL !.rr r,p- 47.
2q. D.r.. s rrner ard reynord I . ! Ls)r "1he 6yrt6.tlcidFrtirl.dtion of orqani. .orpound.", Thlrd edltlonl:tc cras .iill a6k comprny, u.s.n,r 1c54, p-l55r
t:
I
l
-!3qaii
20
22
24
21
2n
ll
45.
!!Lt?
5
t4-14
5
13
t3
2
a
1:l
l7It10
!i_lLl
PotassiuF Prrrar_
l!l-gec!9!-J9!gL
.,30- aJ4q-'.
P6ras3iu0 De.nrn-
atrDle inforratlo.
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