129
cllEllcAL llwEsr IGAT lOlS OF AT{TIC}IARIS UiEARIS AT€ E.ATE SffiIS ,*qi$". L.F{r.rl-rrla |l I-br|ri 5LrL,l trll.t , S.f* rta9 , "+' " €.,r *'
cllEllcAL llwEsr IGAT lOlSOF
AT{TIC}IARIS UiEARIS AT€ E.ATE SffiIS
,*qi$".L.F{r.rl-rrla |l
I-br|ri 5LrL,l trll.t ,
S.f* rta9 , "+'" €.,r*'
\.ycEcca& ttvlltlalttofa
otllltcalatE r-'{q46 eIO lE|littD SiEtts
!ylar-ol lltDld &.trt .
A tt .ir adbltt€d ro tha Ud,e.lrtty ot'rhdfor th. d.g:.e ot Dcrs oa rDltosoFy r!
cb-r.try-
h.ll.tut€ ot CEats,Ublv.r.lt' a! arld -€.tt-b.r lr9.
ACKNOlfLEDGI14ENT
The .utbor dshes to eq)!€86 hte Ehcere 6pjpre-
ci.tion fo! tb€ lnvalu.ble advlce dd guiit{ce q1v€n to hlnby ;lofessor lr.A.Kazl Dlrector, rnsttrute o! Chehisrly,Un1-
velslty ol sind, thloughout this rclk. H€ 15 .Iso grstelulto hin !o! th€ encocag4e.t he received frm the ro tlneand the facllitle6 placed at bie dislb6al dciDg ule erthe
He ia n1gh.ly obtiged to Er.$.a.Naqv! Re!de!,
Institute o! chaistly ard profeEsor B.Lythgoe F.R.s. unlv-€rslty ot teeds. u.K. lor uB€ful sosoegtioE sd inrerpret-atlon of ln!!ded, N.r4.R and Mas6 sFct!3 of 60@ of rhe
cnlbuDds i3o13ted.
Hl5 th.nk6 ale alao duc to r{!.xa1r Abld l€cturerdep6lrftent of aotdy fo! rh€ 1dent1lle!r1o. oa th€ pta.t5.the h.Ip lnd co-or*!6ttor o! the fr@bels o! th€ teachtnq
6t6fl and the aitnintsrlat1ve s!a!! o! the lDstl,tute of cheh_
1at.y, Uhiv€ra1ty of slnd, i! lE.t€ful,ly .ckMledged.lh€ Frk va8 dFomor€al by pakist.n Coucj.I of
Sci,ertltlc anat Indq6trtll aeredch under 6 Schtu Dctmlcltrnvestlsatlon ol aD challE u,n6G1s &it slrlEa Lutea! Tlr.Itnaoclal .ld !6c€1ved is .cknour€itged rith thant!.
ABSTSACT
Ihe tbrk d.rcr1b.d ,,! thl. ttE.tr coopllr.! oa
ch41.at 6H1lrtion of .!!!4C!!Ilf_!1!!!S!9, A'ttchltl,r dr&-j!g!99! sd scruclnluthi! .!th*!e.!f. tt .t.o aL.cllb.tphmcologlcal .tulues o! rh. Iflnclpl.! l!ol.t.c fr6]L4!!-ctE!16 dl.!dulo...
F!q! rntichtll,a tt4str, tr tryatrory e!tc!crl tro os r.F. 123-24"c .rd ctl HZO otO s.p. tA2-a3oc p!@-laloDauy n.Eil s ,ot1ch.!.Ff sd L1tr€...trot r.qxrtv.Iy,bav. be.n 1solrt.d. lle ltrucrur. of th. h|o cqilouad. hrv€bcci esr.bli6b.d r,y chddc.l .r!d rEerr€@Etc a.iit nc..aoth th€ cdtbutrds b.v€ e l,llit1oit .t!et!!.rlt!.G.rct !€rr9. P-gru6side of .ntj.ch.!.rol. E€!1d.. I crlEt.t ttn. lptyhydlor<y c6:buil €ail .r dlDrtltlc hldrocut h, tO€atl,ll.d.e runnltol lDil trlrcotrtd. !63!..'ti.v.l,y? h.vc tl6 b€.n
Fr6 Atrt1chlr1s dl.ndqlo.a, r ..ieptn ca6162
ol5 te.tatlv.ly n.seil Clandqlo.lde |n.D. l3!-35oc .nd .s .ctdc2?lta6ol2 te.t.tlv€ty n&.d u O.l.ldulortc .cld r.p. lat-asoch.v€ b*n 1go1rt.d. rh€ lcrd h.. .I& b.en atlldtly obr.Ln.don dk ltn€ hitLol,y.l6 ot gl.ldqlo!1at . Th. .c!d .E!E r. lobe clo6€ly lel.t€d to glDitulorld€ rlltce otr .ctd hy(bolyatsboth lEr.lah !h. !.m Astu@ .ra th. .q!.! retds.r..tatG!
. Er&oc.rlon liLattal.at .. lDtlr.c€ot.lr ll.. .l.o D.j
lli. Dlxt!.c.loglc.l .toill.r d tD. v.t !.*rat ol !b tLlt .d F!. c.lp|!a 9!,rdulorlar. lf, .io lorttlv. lidU.e. .. !.0.r{. d|. ryFdFatc Ettvttytr coaccn d lut It dld .b{ .trotg torca Drotlltl.a ard
brood c..guhtllrs ottet rbr hj.crrat lnrlqlrtto.t.Ilyto rabLt& lta .!rrl, iU.d ltte t r ioi|r. of .ald.t!-.'.tlo. ol tba a.ug.
lrd Scll|.lDlufthLl .DL.!ocrrt. I r.tur.t d
X.toD. ca? q: o! !.D. 120-z2oc r.. olr!.h.at. a.dib. .hlll|loc.rbt l(Lrtlfl.a |. br.l@t.|!. nr .l!o l,or&.d
coxtEula
l. rxtRolirqllc.r Ea&I -14
laF o
!!na39-70
?1-9r
2. CBACCTaL l,|vlgttcatlo! o!rttancl$Rls lrIStaRrS EEESf,
calrlcl'l rjcvlg|llqTtod otNECATT|Is Ca.lrtrrEa^ rscEitl
rxAuacottoqtcNr a:[tDtta otN!ICAI||!5 (lJ,raEr4sl a$Aal6
cBu{lctL !tv!sal<a|.(l! oF6CI"III|FUN:IITIA 6PE'TIAOCTREA A.BT
6. nE ERII|CES
7L-79
80-9t
92-lot
loa-120
loa-112
!13-120
l2l-124
INTRODUCIIOII
a nurbc! of pluts la thc fom of lDyd€ls utd
d€coctloE hlee been u6ed by locds lo tbe tte.rrnt o!Dhbetd ueUlts slnce a long ttft. tt hla been cldredthat theae drugd lhor co!61de!.ble r\|FoglyeErc .ctlv1tyon 0161 .atdni6tlat1on E d ln 6orc c.!€r hdv€ .ctu.llyFevent€d o! csed diabctes. In .baen@ ot .ny @nvl,etng
sctentlflc evld€nc€ rbout thes€ clal!6 1t vould b€ dllflcultto rccept the actud efflcrct' o! th€6e ,rugs !6 htpglycsdcag€atu nevelthel€.! the <rlbitlty of or.l tlElapy h the
tt€.ident o! dlab€tea cadot b€ werontrhuted. Oulte !fer cdtttFunatg and pl.rt trelEatloE h.ve been u6ed ln th€
rut for th13 tNlFae. Recently G.y Bynthetlc o!.11t .ctj.v€hltbg]yc€nrc ascntr h.v€ b€eD 1ntloduc€d a.d !nl. h4 had
a t[ofound effect on the ttElrpy o! ilia!€t4.D',.lates oeUltE !3 r claoDlc dlte$e {hlch 13
c.'r.eil tt' tho nultlpl€ dl.trbaDce. j,n th€ h€t.!.]tc pr6.-Er€. of the bod!| !€aultr.Dg In u ilib.locc b.iren tb !!.uunlequlreretrt ed the luul1n Droiluctj,o! 1n th€ lodt.coE€qusrlytho.e net6botlc dbholelttles ee orr€cted t{ r€sura .ddnlE-tr6tlon of 1D.ultB.Bor6v€r th€ lEultn ultt.L€ 15 usu.llt !cco-
-2-
rP|al.d yltb hlr&da xht.h 6t tln€6 b€coh€ velt uwtcoo€lha thele 13 .lrayr 6 .tlong cue !o! s€alch o! .Rqra11y 6cti,ve stl'att6b€ttc tflnclDler tEtlcqhtly rted0!61 ldt.kc o! tnaul,ln h!6 i)twed lnelfectlve.
rrE tryblt&ce o! llst€ and h6b6 a &ug.c.let b€ uaileroatleted. aor cotrlea they hlv€ B6n€d
huentty ard hqve leilucsd o! t€IL€ved th6lr agony lnd
tD1n. Althoqqh llL€ nDdcln d!ug! !h€!! pbystologlclt
8nd Fh.nacologlcll ltqdy i! rct ealldbt€ .s 4ch tlEr.rstEctllctty oa .ction t. .1rat. doubtlql, y€t tn lartqat€6 ttE.o rEve bc€n losd very $€fql. It 1r otr.to@
!!@ th€ volk ol c.v.At(rlp et.!l: oa A'dl vt.nss!,slddlqul et.!I: on stept!.nIq @phduth. uit vgg!!!g!!!g ! t€rb ol chlE thlt !.td dlae.r€a I1k€ !€NI clF.
l1c? hitlrteElon anil tub€lclorl! co @x b€ !uce..tu-lly tleat€d by Ee o! tlEee hsbr. so !a! o.ly 2-3 F!-ceat o! th€ boh pLet! have b€en chsolc.tly e61ned.td tt€.€ u€ rey htth€rto erel.rr€d p16rt., 1.v6t1-g.ttoh o! xhlch @ulil Drovc u*!ul 1n th€ tr€atftent ofldre o! th€ at!€aaltql aU.64. U.k€ ce@!, dl6bete! etc,rhtch h4e mt b€o @nqqe!€d D tu. At lny rat€ th!!.tudy t. Flth.hl'l€ slrce tt rLll oF! !€r horr.FE to!h€dlco] !€8€dch ed FuId tlElebt 91ve n€r horE to aul-!e!1ns hq.d.ty. Ch.tn. ho! taksn 6 gleat la.d h t.pptnq
thls gleat mtulal aosce and thel! rclult3 have lren
esry ercoaaqtns.
The loft! plovllc€ of shd. tncluaBng rn lr-Pur atate 1, vely wll Inom to! tt. llchnera ln th6
n€dlcr.nal 9laat! o! vul€d Gtue. 1r lplt€ ol th16 gen-
€ro.tty o! n.tue thc !!€. r6.lEd ufuxplo!.d 6d 1tloE rclk vu €v* don€ lt rd oa ta€U,cltrdt Etu€ ttoC
alr'bEt neglltlDl€. I4 1964 . EcheF sa! d!6rn out 10 th€
IiEtttut€ of chsntltry o! thc Udvolally ol stnil ,lthth€ €4€ratao! ol a6k!.tc! coscll ot sc1€ltlflc 6nd
Irdultrtal a6loEch to lnvostteate !od. edtclst I'Lstsot th! !.glon rhtch h.vc be€D u€{ a6 otiaUcbetlc dlqsa
1n thc lndlglnoua Edtcln.l. aystd. Ihe IE€6€nt srt ias €lfct to lDt€sugate .qE ot tho.€ Inota rblch a€r€tplted to hav€ b€€n u6il by racar! fo! tlE tre6tn€ht
ro t€91n vlth . tlSough .ulvey ot tlE lttellts€,6€ @nilqct€il lail 6 ll.t o! @dtclnd pleta h.a b€en
P!€DaEd {hIch bsee b.€n q!6d ln on. or othe! lom lntlF !!€at!eDt ot dt!!€t6. 1n tlF tndo-rak1.t.n rurr-cort-1neat,. Ih€ lol,loehg t6bl. gtve. th€ Datu!€ of tlE !F-c1e! dlb th€l! Ioc.l neE6 €nd h.b1tat, r'1any locll FLltlatlave b€en lDr&nlILy @ntact€d 6ndl th€lr aalvlc€€ rouqht.
Identtllc6tlon ol th! .qgge.t€d vdltte. rEs iloe .t tbe
botey &p€rt4nt o! tlE UnlE.stty ol sd!d.
t!Birt. I
A,TIrllttiElIC rl,r\Ilis.
E41IT g.b1t.t !aI!
| -- Fclopbur_I r***'l(sindhl) |t'-l'lo"*", I
llce.rdnl
-"1I
(:{lndi) |
(GoJ.at11
;":_..1.I
Ict6k3u |, ]
rgyPt.
l(rndia) |
Eensar. I
i364|
"tI
pt6t l
(tdills)
rndo-!€l | --
It xttl b€ lnt€reltlng to not€ that ou! o! 48
.Fcles U6ted 15 ue froh the scrophu.ldte€8e f.nlly,l+tE6t1y thi€ fddly cont.lE 6ft ffin lflbclple!rhlch e:rblblt !h€ !€iD!t.d hn gl,tcel'c &t1v]ty. v.rlo'r!Dgllers of, thls !&11y b.v€ alre6dr b€en €srtDeal aor !h€
Ple8e.ce ol gly@61iter, csbohyillate., .nd other cadld.ct{ve plt nclpleE. s. J.retrky and h.ulrtchf c{rt(d out
. thorouqh rearch ot the tunib€r! o! th€ ldtly fo. q1y6-
a1dea, Alout 6e !'F.clGq.!€rE investigated and Eny {ere
fourd to @nt.1n c.rdloactlve qlu6stdes. n.Gonzalez5
Gonrll€z 6Dd R.cd€ro trol6ted .9lu@51de !!d cd.R:!1et9:! ehere!6 susMu itula](unl l6olat€d ! nd Folyflu-ctoson velonl.cl' flon th€ !@ts o! vg9g!93_lpg4a ed 1n
loled Botc6-Inr sroda ud x.zimlera Azcsztud lIEoletblt€d e 4t1ery rItEIoId Actlve tslnclples fron6l!9l$lg:la and tbe phsh.coloslcll .ctivlty of rhe
aquouE exi!6ct of the pl.nt *a3 .elEted to crfreic .ctdcontent. lh€ Fl), knoen dl,qtt6lts group ol glycosj.d€6
h.v€ 31& b€6 Isolated !!ft tlE slEcl€s ol sc!oph!le1-.c€& f4ily.AltlFqgh pbuneologtc.r atqdlea on th€qqd€ extlact6 of eE ol the alove pI4tE hsv€ b€en nal6
dt dtff€!€nt contr€a ln the costry auch Etudlca on pue
.ctlve lEtnclple6 s€ lot !vd16!1e. rt c.lmt the!!!o!eb€ srtd sith asgurBnce th.t the !e!b!t€d hytrElyc6tnlc .ct-1vj.ty 1s actuEtly due to the6e p.inclpl€g. Rece.tly
Slditlqut artl lihafl i6olatld a actlv€ hytpglyc€tric p!tnc1P1€
'x€!6un' flm th€ !ru1t6 ol rcrcldic. char.ntia and h4€
de@n6tlat€d 1ts blood sugr! fo{€tlnq prop€.ty. ltowv€r,
1t slll rct ba out or pLac€ to lev1es bltelly soe o! the
srl< done th th€ fi€ld of olatly &t1!€ &tldj,abetlc !ft-
Thc h16!oEy of th! o!.11y .ctlve bl4Dgfyc€hlc
3ubst.ncLs b!g!n5 rlth th! obs.lvqtrons or liatds* j.n
1.116 that guantaltr€ loucls th€ bl@d 8ug6l ol anlo.l6.
Llght y!.r. tBtL! Fldk ona r,r. eseocrrt.l0 inttoduc.a
.D o!a1 abtldlab€llc p!.psr.tlon synth.11n, rl{ch i3 th€
d.cettrylenc de!1vat1vd o! gu6n1d1te. Beau6. of local
1lfltatiDg effecte in th! sstlolntcatln.l'tiact .nd
th. 6usp1c1oD ol liv€! dqag€, th€ cu.1cd tr1al6 o! this
rnst.ll,al rlrd 8ho.t ]lv€d. In 192, 6 6.rles ol blgulnld1nes
rele synthe-elzeit dit t€at.d on anldls for tt!.ir hlttgf_
tc.nrc 6ctlvltlcs;' beclusc oa tl€ €tldbttlon of 6.VGEB
toxlclty theE! @spoqde u.re not te.ted cunlc.Uy €t
that tirc. tioeeve!, 1n th! lart d€crdc tntcrest 1n gurtrl-
dln€s hav. !€6 t€arak.nc€ ad a nqrb.r of &livatlv€6hlv€ b€e! rude 4d th.l! qtllity clinicsUy t€sted.
ln 19.12 Jabon and 6-@!ket!- r.r€ us1ng..n€r
sulfoidoidc d!ug, syntb€alsed by vonkehel and ,.ltrerg
anat obs€rv.d tb€ oessce of s€lerc hyibgllc€nla h ttEj !
Ft!€ots, (sp€ciallt 1D Forlv aoallhod lttlividoar3.
-9-
tb16 drug rs 2- (Fe.ircb6nzol-3utfoneldo) -5-laopropylthlodtazole? u6ua11y r€!6!red to .6 I;rD. Dull.s the aeat
o H N:NHN,1/ \l-l-l I' \\_- / I \"r,
IP1]'
/c\
f44 yeals bubatlelea sd h16 sroup inv€Etlgrted th15 and
othe. clo6ety r.Iated cdFuda tr simals. They auc@eded
1n lst.bLlst)InE tl4 b.slc phalrocological .ctlons of th€s€
dlugs 6nd prcFg€d ttE tlEory that th€y l,@€r bl@d euge
try re1e6slnq 1n6uun fld the b€ta celrs o! the tscleas.No cllnlcal trlalr F e undert.ke! {1th IrtD qtll about
1955. the e.rly rclk of Loub.tte.e6 ra5 conflrhed by I,a-
b.r!€ ad Req6r ih Berqi6 ed btr chd 1tr unlted st.t$.Atdn no cllnlc.l trlar,a r€r€ ln6t1tut€d, In 1955 thcr€
apF4€d a seri€5 of tFp€rB o. ttE synttFals. hlTDglycttLc
acttvlt1c5, phr@cotoqy, ed cl1n1c.l appucatlon o! dothersqlfonelde dellv.tlv€, the butyl-u€. of tEE-s1no .ul,r-
6nUd1de, krcm a6 Bz 55. soon.tte! cdqpoud D aac
or lolbut.ndat€ r.s r.Ieared !o! tesltDg edty 1n 1956.
ocotl
"f4 \! _l _l-l _*,_Gr2_qr2-cc!' \\:,/ [ '
o
-lo-
az 53 (C!!brtoIO.)
OHOH| |
a - N - c - N - cH,- cH.- cB.- clli[-
D a6O oolbteld€)
Th. nor€et labea ot th€ 9E4p lm ta g€!.r.L ur€ t3 tlEt@Iaol,!'] .blor subBtltut.d derlv.ttve, chlor-prop.hlde.
oq ottltlltl
H3c
€ - ! - c - I - cr{- ctt- ctL- cH-
Chlolo lrcp.rr.e.
AU thes€ ilfug. hd6 troved u.eful b{t (:}o tocelt.Ir qnrelcqE a1d€ €flcctr they h4. rt b.€n .cc.tt.drlttEqt r€6e!v.tton. rhc il4g3 tDE€e€slnq th€ D.r.-.Fl rcglouP hs€ .ntlbrctsltal Ft€Dcy, uhich l. lts€u 13 Dot
. ale8lllble qsrity for long t€ri s€. Furth.! .lt.rglc
cl
re..tioG sele tr€q@ntly enco@teled lath this thellrry.Ib additlon to the sufplDnylule!6 $d biguanldlne8r
th€ $1m acld d€rle€d frft the pl&t.,Bl19h1a sapj.d!.
colloqulally krcm a. l!99 ir Jd.1c!? has b€en roadto €rhlblt plonowrceil hylbgLycedc .ctlelti: H.SBA11 and
2ocsrkers er.tracteat rr@ the seeds of the skee 9ldtts toxlc lDlr4Flrt1d€. rhtcb th6y tu€d sl4Fglycln A .nd
ltypoglycrn B the.tatter b€lDg Bpptu{mt€ly hsl! 6! !o)dc
!s the torer. HytDslycsl. r.s a strlklng [email protected]
proFlty of the d!ug, the blood 3u9E l .liablt fellto loss thu 20 mg. tF! tOO ml. Hott lnd LeFpsi; have
.eld,cbs.cteri6ed theee rtelhts cr61c.I1y e . d!'cllc 6nito-/
od tts atttEPtlde rlth glutdic acid, Th€ gen€lal fofruhNy b€ .epe6eDt€d a3:-
H2C ' C -:-/,CIL'%;
oH !n byrrqlyqla A.glut6iic actd i! hl4t9llrc1n B.
/cH2- GINH2- C
Th€ 0!61 htlDglycdlc Egente d€sclltEd .!ove u€
€Il cortbqnd8 cont.tnlng b.B1c nltroqen, 6ltbouqh lt has
not b€en €st.bliBh€il th.t tbe prea€De of rj tlogon 1n the
Btrlctse 15 n4es6ary for hylrqlye4lc &t1v1ty or th.tsulphodyl u!G! o! guanldlne !€Eldue t6 esseDttql !o! such
an .ct1vtty. A ruDbe! 6! rcn-nl'tlos€neous cstpud. h*e
b€en 6h.sr to isless blood-sqga! loFllnq elJect.
I6amedun phosphtG, t@nltol Bnil s€.Ilcyllt€a all taeb((n trl,.d Dtth 6uccrsa !n cLEtll'n @<r-
The q.€ of slllcy1atcs 1n th€ t!€atrnt otdlab€teB 90€6 brck to 18?61 1t $as dldoDt flon i:he {o!kot ff!t3l;_ {14?s) tlFt the re.ult5 Ele uprdtctabl€..itlnconGlstlnt al,though !t ttrcs siEctBculu. R;ccDtry thtelestin the ua€ of 8.11cyl!tc8 1n2d1.bet$ s6 rdlv€d 16
h91.nd ty Relil .nd corlkels (r95s). ah4y ob!€rv6d rbo-
lltloa ol gltcosql. .nd attllm€nt o! @!@glycdi. 1n
so@ IEtleot6 but th€ rdv€lse slde elfectE of ..Ilctrll.nue!€ vely .t4sst. Arcth€! lntele5tltrs ob5€Fatl,oD .etD-
lted liy th€6€ rclk€ls *68 ttE a€@irtg pteothll,ng eftectof c.lclq s.IlcylBte sheD Med {1th dulp}Doyl u!€a.
th€ develotrert oI th6se dlugr he€ c€rt.1nlt.erveal !! enuvcn . mqltllude ol Lnv€EtlgatloDal aFpro.ch€B
to dtalete5 h aU its phlres, aut a trurb€! of lsiFt.reed to IL stuitted b€!o!e a 4lor blelkthlouqh t3 to b.cniw€d. .iblle ttE lrby8tologlc.l ba€16 of the blooat-8'rt!!
IoGrlng €!!ect Is tst1.!ly u4d€lstood thele 16 yet $o
lndlcEtion a6 to the Eel,atl@ ol chealcal stlqctu€ to the
b.stc [email protected] evdts ln lhe c€1] ehlch @mtltuto the
p!1Fry .bl,ecular €ct1on of th€6e d!u96. rhus the Etudy
of ttE rectErr16h of th€ actlor ot tl€ drug t 6alblt .t
ml€culs level rlth r€ltrct to 1t. .ct1ve grootnngr
r.oulal !e ol I!@86 vdu€ bcto!€ q.tns tt to! auch
clEonlc al1@lalsrs I1t6 dhb€t€a. In lny cue th€ id6.!drug Fulil b€ th€ oE rbr.ch lctr 1r the nEt|'d tb.t th3
mj.!M F..lble &t1vlty t, coultl€al Yith lhe b..edolnltM ol to:clc!!t.
the rclk do.clib€d ln thlB thells cc'.iDr1.€. olclemlcal lN€lttgltton of thr€6 lFcl€t of the lcrqt l-orilc€e tdlll nd!€Iy rtrtlchGr1. Ilne6lsr drttffilblarrt-, antlchlll. g0..ndulo6. .nd sctn eldsth.ta .!hl.-roc.ttF. lltee tbt€€ Plsts hree b€€n Eed t'y locrr'. ..slEcillc tfe.teot tor iL.b€t€. hdlttq!. E!lo* h.r D€ct
4ale to [email protected]€ th€ rctlvo tslElDlea dla to ttudt' tlElrbylogrtcsnic etlvtly otr oao hlttd .ud tbel! ltructa. on
th€ othe!, lpFluUy tE lag to tiiril aqE @!!el.tlon lft!€ ..re ts tb€!c. Altlbugh tlE n8tn eort tetDrtcd cotlc.ru
tlF th!€e pL!n!! n€nt1d6d 6!6r€, ! cdrPurtiv€ !!uqy o!
tb€ r.t€! €!t!.ct ot n!t|y oth€! .I'€c]teE hde .l3o b4n
Fa!e. rt h6s b€€n losit lhal sltt€ ! !4 ol th€e cottt.ln
,i.nDltol .tril E!n€!1s lnd Plo.Plst€ ront 1n tlE ',!t.!€:Gr&t. 9qtt€ c{celvibly the hilb9lyc€o1c lctlvtty ...o-.t.t€d rltrl th64 dst. i! due to .@ 6bist1otr ot
!h€ etlve ls1rctDl€ rllh Dnnltol .nil^r tb€r€ toF. In
6oe c..€s th€t€ t!. a dld r{@d toF!1tg €I!6ci .rtl tnotbels tb€ €:(t!!et r.. !o lordc th.t tt clueit d€|th aft€l
:tt!
!.| hol!. rlh.! trjoct a t0 t.rtlDe rrtr o! raDdtr. Dot!-Ir.d ttrn Eorogd.c.r .to4r Frtd tlsrtirc at!lt.! llfotr-tlon .bqrt tlr. .Etu.l uttllty ot ttra. litrnt tl tL tr$rtmht of dlrtb.E!. Ih. F...nt l|ort do.ortb.. lrtnly tblrol.tLo! &d .Eruclold .tucr.iLtl,oa .t!att€..
-t3-
Clul,lctn ITMSlIGAIION O!AI{DICUIIIs LINITRIS H€II.'I.
rhe Fl..nt lgg!9!!I;E_!!99!I1! slda on the h1ltaol lh4. aoL. I<h6 o13t. Ddu) .id 1r dso lound scatt-ersd ln the plal.r ol t.6l@lo ed iahalr![r tn th€ iofnE!
tEovhce of slnd. It !3 su.l'Iy .v.U.bte !n th€ rcnth!o! 5eplqdbe.-octobe! .!ler the Bl!@r ralr!.U. It lg
lDtrl&ly q.€d by rocqr! aB ! cu€ !o! iB.b€t€! D111ts.It b.longs to th€ ldlg Glophul'al,Ae& ald t6 tts€t! !ed]l enu.l vlaclal h6rb rltb s!e.. cyltndll,c.I rodystqn , llne.! lGrves sd vlolet lld€!!. Ih€ EeeilB a!€ Efiltldd obloq lh ahaF. lbe nolrl rire oI ttE pl.nt 1s alout
6' to l+ ft. rh€ pl.nt rur€ blu1.h bl4k oo ikFess.rleliFln.ry pharn coloqlcll .tudl€s o! the a!ov.
p1.nt leve.I€d that rh4 e.te! extlact o! the sanl d!1,€d
p14t ,a3 lnj6cted to !.t. .ttd dog!, lEk€d vul.tlo!6 lablood pres6ure u.!e ob6efied anal ln !€s cAB€! ltlnulatlonof h€.!t ,.a .Iro iot1c6d. It va€ ihe!€for€ oELdei€d€rthrMle to lhvertlg.te th€ pt&t .hdlc.Uy ln al€t.lllnd to t8olato th6 .ctlve tlllnclpl€! rsEtpmlble fo! thj,!actlvlly. llrthd pl|€m&oLoglca! etudies of theEe irlhctPL66rtU .lso atlr ll there 1. uy blrpoglyc€nic .ct1elty
Acohol BotutLon(i|li€d)
-r5.
!5!oci.ted vlth. tlgt .!d rn cD€r .!t, od tbt€ c€.rld lru.€at .r .t! o!.1 .ntldltrb€t1c .g€!t
In€ llLidj.ag .cha€ y.l .dotled lot tb. t o!'.llooo! th€ cqrtDud..
; .r@rDr
Dldt r€ltdu. 6
:De,t.etb€!{5o-€&):
tlet roBldu€ flltrrLlrej.ct.d) Edg$r
4Ltr.!a [email protected]!chu61
rcblololoa!
cr!.rofom rol. Fe.litu€ 3(drt€dl
1r."., '.tlryl a.ot.t€
Re.lau. 2 FUtralo n'€.ld'r€ 4 tllts.taI4!eggl_-g_ ^ntlch.r€Fl
. r.!@l!€rpl, .l6lDI
LnnLtot qllE9lr-e..I|lrete
119.1 dt1cl6.t6cotiected fls Th.n6bul6
llnedl6. tlochBt.l.ha! ln th€ mntb
-16-
rntlcha!.Dl e.6 obt.In€d flqr ttE Fre! eluble poltlonol the chlorofor !!.ctton (!e!1d@ 1) o! lrs6hE thlough. colum o! .l,ulm tdth b€@€De as th€ .olv€nt. rt rttcd!t 123-24 C rnd !n!t y...it lor C1l nt6 05, rJlnedenol rasobtalned try !6f1uxlnq the reatdqe 3 rtth athyl acetlte!!o{r rhich It clystllused Inro ehtt€ n€€dt€! m.p. $2-1E3oo.
It ro.Iy.edl lor C,- x^_ r_-. abth dtlch.!€Dl .nd tlne!-roDl, rplEaed to be cr c6!Dun<t3 sj,Dcs th6lr inotEtlesrnal phtlIcal char.cte!6ltcs djd mr ofr€lpood rdth eyol tho.e coorosd! itesc!1bed in the Ilteratlle ytth lab@Iecuie cdnF.ltlon.
The lcaldu€ 4, .!t€! lsolltlon o! ltre!!€@I, s!dlslol,eeil 1n rlt [email protected], corcGntf6ted -nd qool€d xhca !b.o.lle Itkc c!y6t:ltln. goducr r.p. r63-6ao4 sLp&!t€d.tlr€ tfoduct loflEd . bss ccsr.t€ lnd . hes benzqte .n(l
6rb*€d Fop€rtla€ o! tDly hyd!o:q' d@lEt. rt $6 1d.ntt-fl,6d !6 'n.ftltol.
.Ih6 y161d ot mnnrtol r.s neuly o.atof the total, r€l,ght o! tlE p]&t. t{.rnltol rs 61so obt!-lneil 1n tl y1€ld ,hon th6 platrt ras dtlcctly d!963ted dtbrcter. Bealdoe riAnnltol 91q@6e .nd nhose r€re .Iso foulitto !E se.eDt !a the .lcohoL fr.ctlo! rheo o:..eln€d 1,l,
taler chroMtogruphy. rh€ !)rer6c6 o! rh€ ts !uo4s r.s!uth€! conlired rry lellrlng th4 !! thef phoryl h'l'd!-
.zons al€rt v.tlv€6.
-19-
the b€nzen€ extrlct o! tho pL6nt !€stilue 6 o!conceDtratlrg and trrllyinq thlough a colufu or aluhlD.ylelded an Alrph.trc hydrocsbon E.p. 66-68oc. rhl.ch @ulit
aleo be obtathed by dlroct dlg€Btlon o€ the pl.nr sj,thb€Dzene. It 6dly3€d lor c^^ H-^ 6nd fo@d a $ea Eatducr
h.p. 134-35e. Its l.R.Epectfu v!6 .tm11s to that of a
latuated llj,phltic nydlocabo!; the hydroc{bo! ,.. tde-rtlileil .i tllrcoDtue by nl*d @Itlng tDlnt slth lothdtlc6ed€ o: tllacontaner th€ dll€d ll,colbllc ext!*t oo
!€ftu'lrg ulth tEtlollM eth€! .nd then tDs6lns thloush
a cotw o! .Imir! {1th b€nzere !s elust yieldeat anothe.
hy&o,.y cor.und h.p. 2t2-96 c tent.tj.vely DsEd a5 a.tt -ctr4ol. It eaa mt fre€ly .olubls 1! Dst of the @1vot3.n'i $s onlt 3F!!n91y eolublc 1n chroroforh ed €th6noLr
It lored $ &et.te m.p. 15?-59oci
extlact pqrMcd thloqgh r col@ ot .Iurdnr using beEehe
aE elu€nt. rlon the I1!6t !* fractlom a 6a1 sotid @ss
x€e obtliaeft {h1ch f.U€d to clyataUls€ even 6!t€r ke€plnq
!o! trc mnth. h the @Id 6torAge. on dl6tUtation horeve!,
puler ploduct uas obtarr€d b.p. r1B--9-/o.2 m lt r$ tent.t-
Ihe ledduE 2 *!6 t!6.ted rlth b€Ee.e .nd th€
iELy ndcd.c3 ll,neu6l, clAH2golo. the lnfru€d slEctrasrDved the p!€6!ce ol ungatGrtlon, hydro:.!'l and keto
group., It fortud . cry.t!1lrno !c.t!t. ft.p. 12--26oC.
ltoft th€ foU<elng flactlons doth€! ploduct {.6 obt.ln€d
on additl,oD ot !!t.!th6r (60-30-) to th€ b€uzeDe .olutlor.ThIs p!.duct ra6 dorn ln co.Lou! and tad m.p. lt6-l:ooc.It vas solqbl€ in rcEt ol th€ €olv€Dts ed Itr lnfr.redItrectrm ln chloloaom colutj.oh sbo{ed j,lteDse abeolptloD.g
colleqFndlng to hyillorryl ard keto sroqlE.
3t.uctule o! i{tlchrr€mlr-,dttcialcrcl c.. d.. o. r(duces ..rkallne Fot6ss.t6
perNdq&ale .nd dlcolouEla€! blonnd€ io .cctic acld lndl-cati.g the prla€nc€ of uE.tularlon 1n rhe 61ecu-le. Itfo@, . dlac€t.te Cl5 a2O o? h.p._lo5-tot c 6nd a
ditrc.@te C2s H2.. o? fr.p. I..O-l,.t C, dutv6tlvrs vlrlch
ahoes that tuo ol the f1v€ ory9€Ds s€ iEesGlt 1n the
fon of hyd@rql grcups. th€ j,dI!!!€d 6lEct!@ o! edtich-
tr(el 3hov6 Lntenae .bsorptlon colrc6tbndtnt to ur6.tu-!at1on? nyd!o:q, gloop 6nd calonyl fuactlo.. .aU att€rpts.borevcr, to prlFle th. s€inIcalba2oo. and ir{ dlrltrophenylhydrazone o! stlch.lenot Ele unsuccesEfut. lhls soqgesta
th.t th€ colbonyl IunctioD 16 not a f!€€ )Gto group.
,Antlchar€rol glvo6 B F@1tivc hyitlox41c acld t€st' indlc-atlnq a l.qtonj.c o! 6et€! tunclIon. Thls accounts f,o. trcrc!€ oxysor lD the rc14cule. lhe fttth orygen sas very
ll].e]y P.o6€tt a6 ! (rcd3 gldup sLrc. astlmtlon of d€ttDry
g.ouP in dttch.renol s.ve value €qulvElc4t to one retho)ql
,i.Dtlcha€rcI on h€.tinc 6t 150-G rvolv€s c{botdloxlite rhlch Euggcsts rhlt 1t h.y bG a F-teto $ter.Bor{e!, lt .I.o ltbe!.toa c&bon dj.oatale o. hydloly6t6
rlth 2d ii..tt) rbtch 15 ch&.ctcrlstlc rc6ctlor ofp-hydloq' trut€rUd€s (lctloDic .clds) uhlc!! @nt.1n
a ractonL grouF: th. u,v,Ebrclbanc€ of 23&dr (t, rrJoo,
lndlcatl.E .<.p - un!6tq6t1on i. . llng tstlE! supt !t!ur1. atlqctcc. lhe doublc bond 156 f.1!ly lesl6tant tohtdrogetratioa aE tbele en! nesuglble qpt.k€ rh€n kd€y,aalckel ras ucd as a catllysti d.revc!, tqrilroqe tto!.!)rtsrm6nts rlth tve^-troii qlv.. vcry lloe upt.ic ei.thg.€d$l iL.trqctlon o! thG cblomphor€. iitj,che€e1 gtvea
nesallve l€g3l t€5t rhich 6hovs thlt lt !s rot sn unsat-
ult€d l.ctonz: t! dca not srcy colof r.6ctton rtthfs!1c chlo!1d€ ehlch auggests thrt antlchalcnol do€a mt@nt!l,r rc6ct1v. (@l qroup 1, the mlecqle. ,ntlchlreFldoes Dt !e.ct *lth dlazGthane !s euch tre ts hyiForyl
srouta c.Dot b€ c.ally rethtl,.t€d. 5lEtFscoplc datr1160 1tu:l1cate6 ttE Ife66nce o! Ethyl qtoqp besld€€ ut|alt-qr.tlon !trd oaYgen aunctlons!
To b€g1n vltb 1t r.B tlbugh! thlt &ti.harerclhls . t€trotrlc .c1d stluctu.e (l) llnce 1t llb€!.red c.!-rrn dloxlde eitb f.clu,ry on hydrory.ls dth 2 N Eqlpbqi,c
-22-
6c1at 6nd fq{her s}DrB 6tlodg at'erlrt1on n€u 23bl{Jones lnil irhltlhg , rh€ laJlued absorptioo blnd .rr685d-' u6s al@ j.n ke6plng {ith th( .Itndj.ryB of
29 30r€lEclslk .t al and DunceBon that t€trontc qclds tnilllute @lutlors in i,nelt solv€nte €xiit to aore ext.nta3 B-o:.o estels dd Ir g€n.raf tlE FJor band 1n th€
ca.boryr r€g1d my b€ loqnal anl&hele 'Etred
1,650 ard
1.?55o-:
co(c82).cH(oI{}c2H5
(l) (2)
Th. rciecula. cdrb.lti.o, of 6nticheehol r@ found toco$.rFnd slrh the knorn tetlontc .cld r€fe6t!1c acld
(2) .ltlFqth 1t6 Gltlog iElnt Hrs highsr norev€!, thl.s
.tluctur€ had to bc rur€d out b€cac€ tetronlc &1ds a-..
hlgbly eEli8€d .nd glve r strong f€rrlc chlorlde te3t.A9.1n t€tloric acids on hydrolysis ylelit 6cetotn 6lons
,Ith calondloxiite ,h.lte lntlcb.re.ot d@6 not glve acet-
olD undor tb6se @.il1t1on6. The n€grttvc L6g.I t6atlurth€r proves !h€ .bseee o! ey brt€ml,ld€ structure
!u!!h€! uDaatrat€d bqt€6ude6 de not lttlcl6al !,!| si.
_24-
3llorcb!'ilrliL rhi!€ dtlchalcrcI ls !€duced xith 1t .
Ih! .ext Irsslbluty ,a to @r.ider lt a. ! Wlocatluctur€ Ej,nce a luge nunbe! of plant tEoducts cont.httE < adl Y-Eyrcae atructs€a il) & (4). A5 a 6tt.l olfet the 4i trydrory-2-pyFnes (5) rhlch oea a3 thei!methyl cthals 1. DatG. have ihei! emllc 6y6td 6nt)l!.bl€
32rlth thst ol the tltlonlc .c1d6 .trd tbe atoubl€ bond 1B
ltk€rtse rcat6rant to hyitloglnatton. tbat of th€Ee cq*Foed6 also sh€d cdlon dto:dd. on &ld hydraly5i6.
(1) (5)
Do, tl 1t r,3 66ewd thst s.tlchlleel Dr6 I
{-}!yd!o:!,2-2tryrone stst@ (-csli4o3) .nd ln addltlon !
-oti. -rlc\ .nd a ai3 grloup It the st.uctur., thd lt!ml*ulu cfrIp6ttion o! ctl Hl6 lJ5 Fuld .uqqeBt .notlLr
rinq mst likcly dndctrscd rlth tlE Pv!o!€ rlng as tn the
.tructs€ (6) or ite othlr 1sftt1c atluctu€E.
(3)
*3
@lo
-24-
nor€{e!, thI. strsru. had oIFo ro b€ dlrcard€al
aE th€ cdbooyl .lEorptlon of < -py!on6s 1! 1n the larqe
1?00-1?,:06-r qhllc that ot Y-py!on.6 rs n's! t650.fr:3lgain ln the ult!. violgt th€ tonq ,!ve lenith b.nd of
<-pyrones 16 &.! :oonl 6nd tr6t o! 6trpl€ Y -!!,rone6lt &e 250 . .irtlchaleool on th€ othe! tqrd ablorb.
nrardmelly et 23atr4 dd 1ts F!Jo! band lD th€ calbosyl,
!€g1od of lnllarod st*ctrN IE at t6s5o-1, therelole ltcourd .6t Ipssibly hlve 6 DFone rtructu€. rultlE!.35
'l -pyronlE b(h6v( 6s lactoneE toHqds alk.l1 ed dtlch-.re@I dolE rct b€h.v( shrlarll.
It vqs thcleto.c tl.olqht that 4t1cheeDl cotltE!! e!t6! gloup. Tt'. €5t€! s!4p h.d to b€.(Aurs.tuat.dto l€ ccntatlble rlth thc tnf!4ed &d ultrrvlolct data.
The losa of CO2 on ecld hydlolyBls lndicrte6 a ru.ked
p-klto ester or p-.ld.hydo e3ter. araln to slvc dp-o$e-turatlon, m8tlng nuet b€ as an enol,. l$tlcharenol, tlE!€-for€, contal,ns t-\c group ,o,c:c-@2,cttf rhlcb t. a1.o
coltobor.t.n lrod hoth qltr5v1olet aDd 1n!r.4d evldenc€.
Slnc€ anttchare@l do€6 rct react rlth ilirzftth!|!€ 1t
sugE€.t6 that th€ .rcf orygen 16 not pr€Est .E a f!436
hyd.oryI gioul). lt 16 6!10 @t lr€a€nt a6 .d acl'I.te(i.!). It hust thelelor€ bc tro6crt .B o e@1, €[email protected] . thI! accdDts tor 3 oryg€n!, the renaln-
-aa-
tng 2 ole lfr*cnt .s .cetyl.b!€ hydlo,q'l gloqtE. Ht'droF-
altlon gtv€€ a vsy llox upt6r€ ard thc !h!ffiP!.r€ 1!gradq.Uy iteltloy€d. thelefo!€ tlEre s€ Fobablt @ ibuble
bonds ap.rt tron th.t ltr the chtorbphoEe. ,.co@tlrq lo!othe. g!oup5, su.l c.lculatlor {4lil requlle tra lfeaem€
TIE 60 i.EtZ
ln @clt iB 9iv6.
slq l @sit16(O2.6!
6.25
5.A?
7.90
7,9a
4..;6
7.6-a,3s
nu1tl0llc1tvtoublet J=t-2 H2
Doublet F2.? az
i!@let (retrtll ert€r)
rtiult!p1et. unr€&lv€d
Qudtet ,tt= 2.7, t2- ,
sloqlet 1.et6to)
uselolv€d rhunP'Flob.bly -G!2-cr2-
n.s.r. EtEtrs ot atichlrebt dllc€tlt€
tnt.naltvll,lt
1Ir
lti
th€ Isoton .t lor€lt lI€Id ( 4 2'6r) c.n ontv be !tta-
cbed to a rDlltlon -o-clr.!-, lnd tts doubl€t
b€ du€ to al!y!1c couFlilo. rbu€ groP (?) i3 tnatic.t€d'
Ihe othe! td ftcld grotoD ( 4 3.55) t3 .ot vintllc. It
t@ le to b3 du€ i@€Iy to ttF srouP rtd,-cg<, !d d,t
tlL!€fole b, de to th! sloup ]co-o!4,F, lt3 sqpLtng
r€quI!€s a vi.cin.I )eI cloup, lhlch nuet be that !e.oD-
atj,nE at ,t ?.35. ftE lrtte!, 1r turh, 1. .t5o coupled
rith 6 )(lr gfoup. Dhtch th€ line t*rturbetlon thol.to be that re$dtldg et tf 6.a?. Therelor€ structu!€ (?)
coulit be exiEd.d to (s) addlng futhe! tblt th€ qroqP
(o<) .ttachd to c-5 cslles .t l€alt one hydlogen, ',|hu.t
that {A lttach€d to c-9 cllrleE no hvdro9€n6.
t'-r"- "\o
I
(?)
lh€ 6tluctur€ o! th€
(9)
I
co2or3
I
o/\I
*\ r,
I
(8)
dlacetat€ th€n co'rl al D€ coqtlsteal
the r6ductloD o! t.hltng @lution t'| dttcha€rc! 13 6I!0
Itr agr€4nt Hrth !b1! 6lluctuL !s lt !o6!G.e'. hdlac€-
taI qFup c! cH-o-6-."' 1fils stsuctu!. lEr lDeEvcr, vlth-
out aht' 6t.rloch€hLcal lmPlj.cstlon. th! ring lunctloD
hydlog€n6 s!€ piobBbly cj.6. In .uPPort of the aqove !tr&
cts! cH3-c slqnal ehpxd it i6 lttlched to t6rtla4' cElon
.toft, eil th€ 6ttqchftnt of tbe 46tox!' gloup s'q'Ieln,,
ln rst, rts vrry lot r!€Id Fosltion vhlch ntqht lugg€Et
tbai 1t rs attactleal to unsatu!.t€d cdloh' thls {ould
res artlch6leDol has a telttaly hvdio'<vl erouP 'tlGh€dto 1t, thls tE ]lttle sultrisidq thoqqh tot slfec€deltd
that . teltiet hyilro:<vl gloup should 'c€tvlst€ so eslly
r$tlchalerc1 (to) thelefo!€ bGlongE to trE
rcnotclFne 1!itlo1dd. cloE€lv rct'teil a7!nP1ee a'€ ltdlllrn
(11) Djerae3i .t!d trD&tEoF:n€ xbo6e-rGtbvl €3td F!t'_
€clt'lte tBs strcts! (I2l I@uvE et 'I"
v€rb"olol't$)43
(tr) (12)
@263
-tl
(14)
the N'!'a' 'ttd utt!'vlolst 'Fctr!
(l!br€.3) of
thee trldotdt .!e ,14tl.r to th.t ol latich.teEl.the lsbfi trtabtals, !'rurd,err'ce, .edbb, !9D3t&.
te!!.natl!, s€Dt9in, losltt! u4bclrDolid€ 'r€ aLto
cha!..tc!1s€it It tb€ forFtloo ol ! bt.rL Poli'r€! o!
oxld6tiv€ scld byaEolysls. auth€! ih€v drB coloq
r€sctlonB rlth reiF acllb. ArllctuleDol al|o g1ve5
rh€!€ !.!ct1on6 &al lik€ gealPta tt lnaetlbly .l.lDa45
the lkin to . blqe vlol€t colour .
(13)
-29-
l<I F < nol oo ot o !.
6
$
..ESEY:66
F $p ggs s! es Fe $E
r g=lgcgE! PEg
i .$*I-E .c-gF.
-30-
l{aa. aectla.L ltrt.lEretation ol th! 8tluctur. of.ntl,ch!!enoI
Ih€ res spoctlo of th€ cqrFoqnd dtlchc€mlgiv€d 1o'|i at the fouqlng n/€ va]u€s ettb !€latteeatand.r.ce gr€ater tiu .bout 0.03..
15: ls. 2ri 2s, 2el 3r.,
as, s\, 82, lri s+, ss,
zt, tti zs, aoi ei ezi
,zl tol, rcs, ros, rrolrzs, r:s, rrsl r:gl r;0,rsul rsrl roz, rro, rral2to,22e:"229.
39,40,4r,42,
43, a?,9r,93,
141r 149. l5O,
779, 7A7t tga,
64, 69r
94,9r,L23t 125,
tt1,
(r ltrons !rc!r( * B.6e F.h **. brecur4lon F€€])
lh€ !€ak at ny'c 22A 1s ot cdts st.GDgrh. th€debc! of cebon .tdE h th.13 1oD 86 detelnincd !y th€.!'ubdsncL r6tio or cl3 .d c12 ra rougny tr.{6 trrcretorothl'a Fax 1s a8.l!!edl to rh€ iblecura. 1on (r.).
The Flb at 4,/. ra,zB,3t,41 .nd 59 togertEr tptDrto € ri€thyl e.re! gloup. rhe F.l€ !€sFctl,velttgtr€lqttlE f!.gEbrs <+rL co. ocnl, or-cd
",raJ " coocH3' Thc
er.at .tlen€rh oi trE b.r( p"arc at aTel.tbt r*ver redtlrely itue to the €ster gloup drcc 1t ts knoen thrt€ster6 dtb @1et!e! neel€! !h.r &etat6, ito Dt atve
.trons peatr for ve .13. the glealer part o! th€
rtr€D€&h of thls t*ak is probably belng contllbuted
by soilc otb€! @lety. thts plntr to 6 @thyl !Eo?.nd 6 hydlo4r gloup att.cheit to an .ctlve ca.tbD rtd.lho F€6enc€ of the hydro4' glouP3 j.6 BIle.Ct *rnn lrqn1t! chqdetly. th€ I.R..Fct!u 6nd the l@a ltEct.utFlr rt (r1 - tal . 21o corlltu it, Th€ aetlv€ calon!r Frtaps ! te!tj..r9 clbbod atd 1.€. c-s ln anti.chlr-
lb. 1frFort6nt fr.grntatloE
-!l-
o! the rcl€cul€ lon cs
CAca- f + c83c
c-l co.rblnes vj,th the p.otoarl6
rat.! rclecule le.vtnq the(Il -18). rhis oCd el€ctrcD
a-9 lnd !€s!!nge. to glv€t-
b€ €,(plained .6 foUde.l. Th! hyr.lro:<!' g.oup o!o! c-A to ellihate . qeutlal
lon rclecule elth fr,/€ o! 2Ic
Lon luPtu!€r lt bodds ?-a lnd
(lo)
(15)
cz-qi
2, th€ ractc.l(lg) then gtves the lollolrlng fragllerlta-
@2G3
'*-.*-'\ cH" 1 | -o.r. '* ,A-.'52+ ary-- e
.l{l
(r5)
90rdr
(15)
,/. 152
(1?)
(14) (t9)
* \"/
(20)
ah€ IFah .t tq,/€ 152 due to 116) 1. the .€@nd
h19b€!t !€ak ln th€ sFctru rhlch Ir obvlo$ly due to tbe
leFn6nc€ .lrrrllkltloD ol th.!r 8t!uc!u!€. !€xt !o the
e*etxth o! tlE 152 FriL ,,r lh€ l39 Ee.k ln tbe ll)ectr6.rhe Frk. .t 110 lnd 97 .re 6l.0 ltloDg. rhe la.lEEntr (15)
l1?) (18) (19) @nf!fr that th€ t6ltltrtf cubod 1! c-8
6il mt c-6 d c-7. Eor,cr€r, thla Frh.D. qbutd b€at b.
@z@3
€zq!
IEftd b!' the ileutratlon of tbe
3. eother rcde o! tlsSheDtlt1on
cltre j,on 6i+) rtth the los1tlveth€ cdlonyl, in th€ erre! qloup
'{"-*.
-0"%
b
ott
122)
c-8.
(21)(23)
-H2o
(24)
.rcthe! aetleB of
c9zQr
n\/a r7a(25)
f laguFntatloB t. tD..1bl€xlth tF ltlve ch.lgc on O-2
co-cH- cH- I.tT--li " "N--.ty'.,_______r ll +x-o+ \L,/\^/z Y
E
(26)
o,
t27) (24)
NoN .lDat .!L tbe najd ro! pe.l(l b.v€ b€€n 8cc-
ouot d !or. It N5t bc 6lrh.5i3€d lEle ho*4elr th.! htqch a cdDl€x lFl,€cul€ rlE!€ !h€ *6rt1trg rcI€cule1on ri cs bG ploduc€d by €rrplu.lon of ooe o! th€ €I€ctrotl|!16 th€ lo!|€ Ftls on ..y o! the o,q'td. Eiil th6 pl elec-
t!o!6 on C-3 cu le.lly b€coc bedlil€ll,ng ard th€r€lorc
thc !out.! o! l!.9!Fnt!t1on Bho6 !bq,e ra' mt tE uDtqqc.
!|oro Flk !. !€qulled to dl6cov4 un nibt.enour rout€r.
lnrplte o! tht.. th€ €vl,Ccrce lfod@eal lEle ||lld h 1.S.
N,ri.A. u.v. log€ther rIlh thc chsdcll s.k gIv€! $ ealt€a iecq€ .on!1!mt1on o! th€ atluctulg Forored tor
atrqctsc o! !1b€q€pt.Llo€a.eml ulr otd€.tn€d @-E th6 y.t€!
lolql|l€ t Etld.fter th€ 1elal.l,on of {ticlt{€'Flrn refl,or.lng the i€.litu€l{dth ethyl !cot.te, fldrhtcb tt crt'6t!-Lused lnto nedl€! D,p. 182-$t , It.ndFed tor Crl HZs otO &d folrd . crya!.l,Iltr€t€t!.-&€t.t6 CZS%lort ".D. 136-38oe .Dd t€tr. b.!r6t.Crg BIZ ol,r m.p. rto--llos itellv.ttv€!. tt did D! forn.||y derj.v.tj.v€ o! ketg groq|, U.k6 .nt1cb.!e@I .ndg.ve ! tbrttlv€ tva|!:ox!'llc aclil t€lt rhtch ladlc.t€dtb€ lreaeBc o! . I.ctoo€ o! eata luFtlon. tt €@Lv€d
cubon altoxlde on h4trno .t 2to-5o C tb.!h t€r@.!.-
-35-
t!.e) add r€a1d8 crlEc.llts€d r]rd b€ozer lqto €
ploddcr n.p. 165-69 c. rhc plesence o! adlacenr hydr_
o:q'] gloqp3 ,as lDdlc.tcd try Fliodic .cld te!!. rlrneqatlve lodo-tolq\ t€8t 6ho{ed ltE abeeDce ofc.r3,c'o sroup. lts u.v.shoued IEl(r@ .t 236 nrr(L 5oool
ln .lc6lpt rhich t6 typlcat of o(8, unsstqlated €rte.carboDyl g!outt._ UD11k€ lrrdcblreDol lt ald &t t ibelatec&r$n dioxlde on acid byilrolyris. on reductloD elth6odt@ !o.ohy.!!ldo rn dlLute erhll a1@hot tt gsvc scompound heltlns .t ua-2ooc qhlch shoEd dlg.pF!!.rceof cebonyl band 1D the tn!r6!.d. ni,ae6e..t @uld btbe sethyl.ted rlth dlazoEt'bare lrdlcattng lhlt emto:q'g6D i5 mt preaent !6 I !!e€ hldloryl sloup.Hyilro-g€n.l1o! ove! Raney nlck€t ca et auccesslu1 edtfE ollgtnll d'losd H.s !€cov€!€d.
Llde{Gnof 91vee !o.1t1,ve teEt6 fo! gltc-oslde6. on .c1d hidlolyeLs 1t yj,elds . .educlng sqg&rblcb €s ldentltled .s glu@6e. TrE lgtu@n€ r.s v€lyunst.ble a,rd rapidlr .f!o!ded e isof.ble bt.ck afur-Pfpq lovde! hhtrh 16 a ch.lacr€lstlc ploFlty o! tumtErpen€ 1!1iloid3. sldce tlnealeaot h63 . nolecu16!
.dtb.tteb ol CtZdZAorO lts .glFo!€ Fuld lEve thelolmuta ctl Ht5 05 !ft€! ,ubt!.ct1ng c6 sll 05 lor3ttlcheent of . gluss€ urnt thlosgh ! gtycogldtc11ak.g6. Artlcba!€nol 6utd not ho*v€r b€ dhectly
-36-
ol,taj,cd o. a1d bydlolysls. thrs 1. undelstsdlbleette qrilch.r:€lo.1 16 dso )(roM to fqn!6h black tbr-de! od acj.d hydlorydE. As ! mtter o! f6ct the r;R.sPectlr of tb€ IDI!@rs obt.tned sdFeratety on brdlo-lysl. ot l1De.lenol .nd .ntlch6reml !r€ ideatlcar.
Tne rorrutloh of t€tr+c(rat( tnd1c6tc5 touac€tylable bydlo,q,l gloups ehlch !!€ sc@sted lo! t8/
the glq@a€ rc1ty. Ihe.cetate h.s an N.!r.R-6tstrurhlch stDHs atl th€ !19!.I! lrom the 6ketetd, IEoto@of .nt1cbare@t aad 1n ldditlon 6hors stgn.lE atu€ tos!: plotoE 6tt.clEd to c.lbon atoE bea!1ng ac€to:qr
o! sidilar gloups. the 1tr!!!red dd Rss 6IEct!6 o!fln€a€nol ail $tlcblrenol .!€ ..tso sihlllr. rt 13
thelelo!€ trDqght rnlt llnes!€rcrl,e . r-atdolEbsideoJ 6rt1ch6!e@1 6d slDce alMg rtE lrldoLds qlu@se
attachecnt te {$ualty !r B -F51tion lt 6€e@ llkelttt8t lin€arercl j,s tho p -D-glucosld€ of 6nricharercl(29)
!%6r
[- l-"_l\ irr tolorl. -&, orro*
\29t
-!t-
cdtitctld o! ,/9-gtu@tlillc lttikAa€ lE llm'r€@I rt'
obt61n€d br cllryi.ng oul .ttlhlttc trtdlolvart dth p-{d'!n-
*htch funlsbed $tlchdenot !t th€ €Dd tFoduct In good y!€lC
The &tlotr o! thL. €nqm L t.I€clLv€ ed il lt lodn to
hytllolyse only th€ [email protected]€r. H€nc€ linssetol Lt sith_
out aloubt &!1chu€troL-p-D-cluco.1d6.
A nunb€! ot tllaloidl! E€ ktoitn {blch teur aq4t 43
p-srucoslde! Ib Datu€..v€!b.$Ii;: (!o) ' rosslc (r{)
aNubi;v (31) trDFtEot€l; (32) sil Pt@1dtd6 {33) se
6€d€ o! tle ttt4olal! rlro!€ .tlucttE€t aPPcll t' lF allillsl
to ttst of l1rea!€rcI (29). a qsl.ll't@ ol tlalr lEoIFr-
ttes 1! E4vea l! tdbl€ '1.
o- s,hos
(30)
'2(3r)
o -"aattos
co2c83
-34-
HO.CH2 - c-u..o-
(32) ojh'
(33)
TAA!E
(() u.v.0rl) I.R. (cnFr)
ct?Hzaoto
"ts"zzogctlnzooto
ctlH:eoto
cztHzeotz
"t?t2nott
ctoHzzotr(fi2o)
-1?30
-1140
-2ooo
ra2-a3oc
1s2-a3oc
222-2toc
224-2fc
169-?20C
l32oc
2!6(E5OO0)
236(t1OO0)
2la-36
231.5G0oo0)
3620?3530,34OO,t6?O,
1?10,1650
)
lZ93a.3495.3300.3165, t?46,1?{4, 1?Ol,
EXIIRIIIE'IAL
AoDaltq! "'. qt€rlql..
d!€ E1tlnq Flnt! b.e ott.tFd o.r . t!!h.rilolul hot 6ta9€ Eltlng tElnt al?araur d{ lr. urcort.ct€d.
lh€ ullravlol€t atEct!! s!. tlt€b on ! B€clrlln lbcct DB ,Fc-tloptDlodFt€! ltr I a. .tuca caII. ulnt iloqbly Cllllll€ilr*.r a. .olv€trt. rh€ !n!!u€al st'€ctra Er€ r.€.rdrd o! r{r.lca ealel rP-2oo ud p.rlrin-BlE! ht!.coad D(!st-137 Id!-!!.a .FctloprbtdEtd. udlE .tFctrogr.a} I(Br, lqJol .d cbl-oFloh fo! trqElng tFll.t , nqjoL oqlr! .!al th. ,olutldlelFctlvely. Tbtn fi,ld rue t.tetr b.tr,.€n rcd.chlorlaF Pra-
t€3. th€ n,t'r.R. 3F6ct!3 ro!€ obtaln€d on ! v.llar A-60 slD€cllo-
!€!c! ulng t.tranethyl.tl.n a th. trtuanl G&d.ra' lh€
rr.sa Stpct!. rci: :€colil€al oi s iiE.r rs902 4a |(lp Ir.. qF.qrF-r.fa. ttE ot rtc.l rot t!oa! l€s. t.i..! 6I Ettg€!
stdd.Eit !olu!.et6r ulnt . 106!. !|I.!, tuD. .t 3ooc. !t!tl6Ic,o!DI ra8 a€d 4 th€ .olv.nt, Col,'an6 for chlantolEtlt{rer. F.IErd fsd E.u.rck'. .t.naEdlrcdl .Ialn. lor cl|tac-tog!!pht'. slu.c! G6l. o(a.x.rck) r.! ur€d for thtn llts &a-t!.tosr.!tv. aleenlly.l! 14 ca!1€d Nt bI r{/8 allld-B€rDh.ldt ilcro.slyttc.l !.bo!!t*l€. rsrt (5!t t!'.
-40-
I e].tlon of &trichueno.t.
The plut Antt.hsiE l1nee16 (50 kg6.) {s k€ptlnrEs€at 1n 6ld alcolFr (150 11t!€s) !o! tF keks. rhe alco-lFl r$ lelwed t!| d18t1]1,!tlon $d the !€6qttlng exr!.ct eag
d!1ed on 6 rater tFth. The sdhl-solid restdue thu6 obrltDeat
r$ t!6nafer€qto a lound btton ll€sk lnd heat€d uadcr ref,Iurrtth lEt.ethe! (5o-sooc) thlee tlrs to rede trE cblorphyu.nd the fata. lhe restdue 1 obtaln€d after tbe trEt.€th6!er.tractlon r8 ths entr6cted vlth iEt chlololom exhlustlvely.the chlolotom €xt!.ct4r€!e cdlblneit dd th€ 6olve.t q.6 rem-ved h6r dlstiUltloD. liE elvert flee lestdoe ras dis@Ived1n {at€r and flrtered. rh€ !lrt!.re r6s drted, dlssolv€d iDmln1M quetlty of cltlolofolh and .dsorbed on olhlns (!.ra€!ck).
It vae €lut€d llrst qlth benzene ard ther rlth chtorotolh thr-ough a cofuM o! .-tEdnar The [email protected] f!&riois (loo nr) Er€collected {T.bIe 5l
T;BI,E-5
!-3
8-1213- 19
33-35
1
2
3
5
7
-ill-
ru u|. tllctLoi $r.,o.6it!t.d .&tl dlt'.dto crtrtlru!€ al !o.o t.4r!!ttt!.. Inltl.lly I gutrtt!' nl!.!
apFE.d 1n 6ll th. gfoutt! &d dt r a ret cqf.t!.ltltdlonst!!t.al ln qroqp tot. Z-6. ltt.r . f6. dry3 th. cry.tal, r.l€.€Far.t€d frd .ch qrup .!d r.rH thre tlD. vlth e.Ir
t'ltlo or @Ll eth.! .!al trtlFE r€6vstdlt..il lrd hot
b.nt !.. th. Ettttt{ Fintt ot tb' Gt'rt'l' ohdn" 'r@
th€
grouF 2-6 !€r. id€ntio.l (122-12/t-c) .Dd .tDr.d rc abF€tard
vih€n nLr6d Elttlg lDint. x.!. tdk !. lO|. ctlf3t!:lt e!r. csibio"l
eit lrth€r !€cty!t.rt1!.d tr{ tr€n!.m to g:lv. ltm !€€dr'r
(r9.8 9i?.04r) of .ntlch.!.*l b.P. rB-124oc. ttt tElty l,&
cLcL€d bt, thin r.!|8 ch!o.t6{r.dty. lh. cdultto! .l!1t313
gdr€ th€ follovilq r€.ult !-
2.
-.Sr.t-
5?.9
-.E..t- f!h-6.9 34.9
6.9 3s.4
?.4 34.7
7.0 34.9
rh. Dl€cu.lu retght I@ lo!!d to l). 22a lro tb. 6.r. .Fctrolnit th. DlecoLar totuul! rolt d out to be clla!6o5 thlch
lGqotlos c,5?.9, Il,?.0 ed 0.35.1. rt tDtlE.at !t cttuD 3rn'€d
F!&! !t 35oo, 33rl,6r-1 (htdrr.yr qroq!) ,2950, 1690o!'l (corbo4'l
rjioup) ]62aih-t (un!.tu!.qto!1. ta6o , 1425,1300r I lo5, lo?o' 1o5o
960, 9!Or 835, 805, .r*l ?65CD_r et9.3). llE )'tr!.. (tr)t'E
loud .t 23a utr e - uooo)tla4iro (c,lor, at.t Ylt -13'5'
-12-
sbsr39!9€1.e!99!-.Pl--i4&h9r.c!9l.{tl sotubilitvsolubler- !1@r&i, cnlorofom, eths, rater ltrldlne and
ethyf acetate.
spal,DE]y: .ol,ubl,er - beozetre
Inso]ubl€:- Cdbon tetlachlorld€, IEt.€ther ed cebon d16ul-Flrlde.
tl!) {qctlond sroup teatsr- The teats Perforned u! Ehdhin rnElt6:-..-
Ijr-L!-E:--9..
r. lelric chlo!1de.
2. Dil.sodlm blcdboat€.3 . 2 : 4-dlrltlopheDyl
hydlazlo€ teat.4. Hytllox ic 6cld.
5. B.ofrire tn acetic acid.
6. Dlf. rot. lEm&gnate.7. Fo.naldehyd€-sulphr1c
6. Frledet-cr!!ts leactlor
t. Aehling aolutlonr
10. Tlipheayl tet.ezoliueirloride 5olutio.,
13.Pd1odic.cld.
phenollc or €noucrodr glouP 6lra€nt.corjli gnouP a5.€ni.
keto group 6lr!Gt.
cH-co qroaP .bs4t.!o calbo-hydratei
ott gloups de et6 |satr.ted le-
rreb6lat1on of dl-lcetvl ile!1v!tiv6r-Antlch.leDot (o.t @) !n pyridtne (1 nil) ed ac€tlc
attydrlit€ (2 hl), r€re h€ated on e.rer b6th lor trc rDqs. rtea. then c@Ied dd pour€d ,nto lce u.te!. A g!€r/16h rhlteEo11d .pFed€il rhlch rd u.shed €uccesslvely yfth itir. €odisbicdlonat€? dll hydlochlolIc acld dd eater.rt vd dlsEolEdin llcohol/ decolorlaed .nd crFtalltsed frd .lcohol-vate! lntoredl€s (o.04gh). Tbe6€ Ere reclydtalllsed f!@ alcorDl-e.te!trrce. (h,p. ro6-?oc). fosd c.50.3r H,6.2, 0,35.5, c15H2Oo?
!equ1!es c,57.70; 8.6.6r O?35.e. The inf.ced stEct!@ slE ed
!B1n at\sorptlod tEaks !t 3000, 1754, 1705, 1650? r!i50, 1390,
1300r 1240, 1190, 1140? tos?, tJlo, r60, 860, .nd ?o5d_l(FigL 5). Its u.v.n*inE {al@tpl) ras tood .t 233 hl G95OO)
tlerEation oa dlbepzoate &!1v6tive: -dtlcbeedol {0.1 qm) ta pyrldlne (r RL) ed }en_
zoyr chlorlde (t mr) rcre heared rosetber on ,.te! teth for on€
tpu. Th€ re.ctlon n!,xture *.. c@led, rDu!€d tn rater alit the.extracted lith €ttE!. the ethe! solutlor uas yshed ,Ith dil-ut€ bydlocNolj,c acld, dllute aod.blcdborate ahd flnarry vlrhvate!. It v6a drle.l ove! .nhydrou6 soit, dulphate. A!te! ferc-viDq the aolvent the !€dldu€ vas reclystat116ed !!@ benzeDs
IEt. ether (0.03 gh), m.p. l4O-4loc. rouDd C,69.Or A?5.7,
o,25.1! c25H2.o7 lequlr€s c,6a.3; It5,55, o,25.65.
E-EspgrEg9!--e!--gf ir5rU!i!!E9-!9!s94e--Artlchd€nol (0.1 qn) 1. dry A/ridine (r0 d)
sd 3:5-diri!ro t*.zc!l chloride (o.39.) {ere heated on rate!b.th to! 45 rdDutee ed Foued tnto d11.t'l'al!ochlo!1e .crd.
The aqueous 6olutioa ps decated off .nd the !e6!dqe ra3hdt eltbdll.6oal.bicabon.te and then rlth rater. tt re telce recry-
.talt16ed f!@ .Icohol-rate! to dve the dlbeDrdte m.p. 116-
lS9ssP!sq-E5.9ELe!:.9slE--Sg&6rb6zore!-sedlcdb.zlde hydloch1oltde (.03 9r) .!d aotl,
lc6t€te (0.06 cb) disFolved i! 5 D1 e.te!. ,€!e lidded to
etichsrenol (.025 th). |rhe cotteot6 flere heatd on r!te!b.th €nd Ieft 1n @Id stor.g€ fo! . fs d.t6. No cryst6lt
apF.led ed the o.iEh.I ccrnpou.d fa3 re@veled fr6 the
!€act1on nlxts€.attspted breDs.cion of 2 r 4-dlnitro oh€Nl twilr4onet -
,htlchd€nol (0.o5 9ro) ras dlaBolv€d in nlniDm
quetity of ethlhol ud to tb16 vs a/:l&d fteEhry Fep.red
dolutlon ot 2:4-dlrltro phenyl hytlr.zhe In @tt6ol .nd a
!4 dlops o! conc. Hcf. Th€ conteDta r€re h€dt€d ot s.t€r
blth ed Bllded to @ol! No cry8t6lline derlvatlve cPF
esed ev€n aate. k€€P1nq !o! a reekrE tlre'R€duction of etlchaeools-
l1)__d!!b_1i!!1s-3!4l! A rofutloh of antlcha-
renol (0.5 sr) in 50 n! dry ether tE sdaied to 3 qF. ot
lithIq Bludnlm hydll,de. It Ha6 realu,<ed for four ipussith cod€tet 6t1!!1D9 . It flas then c@ted aod th€ €rc€as
of ',lllit_
vas dcstloyed qitb a f4 dlops of v.te!. fh6 6the!
30lut10n s4 liltelqi ed the r€sldu€ e*tfrcted rith ether
(3 x 4). rt fla conc€n&ated 4d left at ldh t4tFratur€ror ts dlys to 91ve vhlte n4dle3 h.p. l48-5ooc, Ihese vele
reclystalllEed tdce frd chlorolom-tPt.€ther (50-7ooc)
m.p. r52-54-c. ItE cdbstion analys!5 g.ve c,63'46t A,9.l2t
.\a 0,27.42- rh'lch do€e not coFespoDd vlth thet of e:qFted
alcohol fld the estd-It sh@ed lnfrar€d Fak6 6t 3450?3300,2950' 1?40,
1650,!4?5? l3sO,r23O, 1r40,1060,1060,535?9t5,900.450,S12 rnd
?606-r (kBr dlsc).
!4ji*!-!9!44-!9!9bl!E!!9-r- ! sorutlon of btichaerol(0.,1 qn) 1a neltEnol (30 hl) 6s llFt c@led ln rcc-e.lt
nixtur€ snd then 6oil.borohtdlid€ (2.4 ss) 13 aild€d to 1!Ao
6hal1 Frtions. It rqs Left st rod t4l.r.tue fo! tFnty
fou! lpu!6 add the c6!tent6 dllut€€ rith 20 hl {ater. eth6nol
r.s evstblated and the solutlod €xtlacted,1th €thyl aqetate'
No r€s1dq6 xere obt6lned lro the ethvl a.€t.te ettlact.
Therefo!€, the solutlon va6 lcldifj.tt rith dil. sulptuElc
ecld and .xtracted ulth chlorofom. The chloiofom solutlo!
,as dlled by evlt ratlon .nd tfE resldue alloGd to c!y5t6l-
l!3€ l.o.blolofotu.Ft,€ther (50_?ooc). ,rlter treDtv lou
-46-
hous th€ cEy.tal8 re!6 foud to bave Eepdltedrthese {e!e.ecrystalll6ed frd the 5.8 solvent 6.p. I53-55-c, Thl6
c.|ntD@d r$ ld€nocar to the caibsd alleady obtained Lv
the leductlon of dtichar€ndl dth LtilH4 4 conflnl€il frftth€ 1d€ntlty o! the mlxed reItLng lDlDra &d th€ lnfrEed5!Edt!a o! the cmpunde fld th€ tvo aoulces.
Bvallol,vs!8 0f artlcbarenol.(1) tlth 1'l H2so4:- Jstlchuenol (2 q@) ud 2N H23o4
{30 ml) r€r€ runed on €ter blth lor h6lf en ho(E Hher !qa6 ,a obaeryed to have 4otwed. It ra tdentlfi€d s ce-bondl,odde. Afte! rhe wolorion of ga sub8ided, 6 bt aik
I,o]the+ettt€d d4n ehtch could Dt !e clt6ta11ised fr*eny 6olwDt. It 6hov€d l.frueai b6nda at 3510, 3ooo,
2SOO, t?25, 16?0. t4,(O, ltso, 1290, rOaO, a4J. and ?6s d-l
(tll |itlh dLlute aod!6 hw&oriile. - ,ut1ch!!ool (o.5 Eh)
and 5r sod.irydroxide (25 ml) rere heated on v.te! b.th fo!one hoq, on .ddLtion oi dil.htdlchlorlc .ctd, Ihlte trreci-plt3te€ app€u€d. The pfec1pltate. vere filtered dd dtss_oJ,ved in acetotr€. th€ .otutlon sa6 treated {tth sni.md cha!-coal, coocedtrat.j antt c@Ied. Ito clysrsls could be obt.lned.the eolveht ea lqmved ed th€ les1du€ s€t for vccum dt€t_tllatlon but e ploduct could be dj,3tuled out upto o.2 E.m
l5CoC. The contents rere found ro t€ charEed. Ther€fole, 1t
Ot1d6tlon of aotich6renol,.
(l) irrth chlqnlc acld:- cro- {l sD) !n dtlut. sul,phullc
rs aditeil to ultcle€no1 to.-S sd ara left at romEnlEla-tu!€. fhe re.ction yaa cffp]et€ .fter ts hoG6. It r@
extracted {ith eth€!, Ihe €xtrdct xaa concentrat€d sd cooled.
No c!y.t.lli4e p.oduct {a3 obtaLned theretoie t}E sol,vent
u& !@vd rnd the residue ra6 €Iuted tlEouqh a co1@ ol!]q1oa (!.nierck) uElng chl,oioforn a6 ttE solvent. A!te!@nce4tratlon of the eluted slstlo! lEt.ethe! $s added
to she loint of turbldltt aad .lIored to r@1r io cold 8to-
!.ge but no c!y6ta16 rele foqd to h6v€ ap!rcdei dullng a
!E!1oil of t€n dat6. iJte! the leFoval of tbe solvent the
!€6idue rN tubloct.dl to vacum di6ttuatioD bqt only ch.!!-1ag t@k place ard ho dl6tlllate could rE obt6hed.(11) 'ifi.th Fot. rEm.nclnater-
Mtlch&sol (r 9n) ra. au!6olved in t.te! (25 in.)and iDt.Ffmangnat€ tn dllute H2so4 {.6 add€{ tUt ln sLtqht
€xcess. the precldtate of naqn€ee dloxid€ va .etdeted
goluble r4, the addltion of sod.mt4btsulphlte dd the.o1-utlon ,a ertrlcted ulth ethyl .c€tate exhactively. To tbe
€thy] acetate solutloD 6fter dlying over 8od. sulPbat€ &d
con.rntratrng a .Lrttl! p€t. .rher tsO-?OoC) us addeit to th€
tbint of tulbldity .nd aft(rcd to .ool,. - cry6t.lllne sub6t-
aoc€ 3€pdated out n.p. 132-35oc. Its 1!f!4ed slFctrm sho-
u€d !b6o4)t1on FaLs at 3500, 3o5o, 1725, 1,{20, 13?5, 1165,
-44-
and 72ap!-'. Itle Froduct {!s so smll 1n qu&ttty tbat fu!-thEr Flk coufd rct be undeltaken.(111) fiith hvat!@en eroxttl€:- Eydroqer Froxlit€ solutlon(25 nI. 30.,.) {$ added to urlchd€nol {r.gh) .nd heated oD
r.ter b6th for tlE* tDurs. tate! 16. lgFved uitcr .€duc€il
lfcaru€. TrE !€sidue es d1s$fved 1n ethtl 6cet.ter 6.c-entllted ud cooleit. No crygtalllne product 6ettlareat flon1t eleD after teeplrg it upto tF reek. rlte plBte obtaj.neat
on re@val o! aolvert H.a .cldic Ln n.tule od ,s v€ry eGltit could rct b€ lavestigared fGth€!.
Attspt€d hvdrco€n6tion of etlcharenot.lll tlth RaDev nlcrrel as the catelvarr-(o.5 gn) ,a3 .dd.d to a Bolutlon o! .ntlclFleno] (t 9D) itethyl rlcolFl (50 m1). Hydrog€n v6s p.sE€d f!@ a eylind€relorly et!i]€ at1!!1ng rhe Bolution rlth a maqtretic srl!!er.Alout 5C c.c. of tb. g@ r.s absolbed in the f1!st fift*r
'nlnutes od there aft€r no turrhe! consuption o! th€ gdrr.E ob6e*ed . The al.olrcric solutlon (s!en1sh 1n @Iour)
raa flltd€d to reFve the catalyst. the solveit rs lg@ed3nd th€ regldu€ eluted thlouqh a colum of 6lhl,na rlth b€.-zene a6 the 6olvent. lh€ .luted solutlon o. concentratlng
and c@Ilng 9.v€ back tbe orlglnal c6!D6d, n.p. 122-24oC.
(i1) ylith alladl.€d ch.rcoal: -The cstalyst {0.1 gm) 9a3 add€d to ! sorutlorri
an!1cholenof (0.5 9n) j,n ethyl alcohol (20 nI). rrydrogo qu
-49-
uaE tlgred lnto the lolottob !o! tventy fou! lDur6. rhe
solutlon raa tiltded and lta ultlavlolet apectla recordcd
rhlch 6tDved no m4imM abeorbancc heE 236 'ti^dlcatlnq th.tthe ch!tuphole h6 b€€n d€stloyed. The ethyl slcohol ra*.tDlEted 4il tie roaidue crystaLlieed !!n ethyl ac€tEt€-
b€nzeh6 but ho cry5tal,6 could b€ obtalned. The solvent r.E
ev6tDlrted and the rcaidu€ Iutft€d by laslng ttfough a
@l,le of alunlns rtth b€nz€he as tlE solvet. rhl€ solutlon
on concentr.ltng aod c@llng gav€ r vely smII qqlnt1ty ola lE6t€ ,hich could not be clystatused !!d lDy cofv€nt,
Furth€r 6!k @uld @t be cortj,aued due to th€ albEtlge of
attspted p€thvlatlon of rntlcharenol.(i) klth dl,.zmett6trc!- n elutlon of etlcr6!4ol (0.5 qE)
ln ether (20 rnl) ras .dd€d to .n e7.ess o! eth€le.I itlacO-
ethabe and left 6t lom tdlEr.t[e ror thee dat8 duing
,hlch tlne nole diazorethao€ {46 add.d flm ttme to tlme.
The solution r.s dli€d sd€! leduced P!€ssur€ ed the Eealitu€
,a dissolved !n bcDz.ne !r@ rhlch the olisln6l cdt und
Attsopts .t th€ methyl€tlon of antlchale4ol Fr€nadc at ooc .s El! es at ?Ooc but rcne ras gucceEsful,
(1t) ,rtlh m€thvl !odlde:- Eot-cabon6te {2 qG} ud mettr
lodld€ h excesB vele.dd€il to a solutlo! dtLch.!ehot(0.5 qn)
in accton€ (25 mI). The contents e€le letluxed fo!
-50-
61* lbula. A Littl€ @thy), Lodld€ us add€d alter tvo hous.Th€ reactlon hlsta.e vas c@l€d dd flrteled. The fUtr.ta14 46t!!atqi to dri4eaa aoil ttE r$ldue cltstatliEed &dchloEoforn-rE!.eth€r (60-aooc). h.p. t22-23ocJl. u.6 titenrl-lled aa th€ oltglnal enFund.Irolatlo. of llnesercl. Tbe .lcotDtt. €xtr.cr lelt .iterthe lsolatioD o! ahttcbarenol (r€sldu€ 3) ea6 leflu:(ed rl,thethyl.cetAte E.v*at tihes. The ethyl acetate rs recover€d
&d the !€sldue thu! obt.lDed rs3 dlssotveal 1n .lcorDl silch.orotogrlpf.ed oo B coluhn ol .l@in. {Ith ethylac€tate alr
the €lq€nt. the lirat lractj,oh (abour 5oo Fl) d1d not sLve
4y cry8talline lEoductrbut fld the aotloriog tr6cr1oE, on
conc€nt.€tiog lrd sclEtchlng the rid.s o, tb€ ttask/ needles
of llnee.nol a€iEated at !@m tehFratse alter tr at!y!of l<eeping. th€ cdrouDd e4 reclyst.rlised !!d ethyl,acet.teto the coctdt n.F. rAr-92 c {2a 9h6, O.O56t), rts tMlty
l.2.
3.
The rci,€cqlEr folmul^ cr?ri26ord:eSu1les c.52,30i 1r?6.s? .nilo.a1,13. rt ie {'d_" -rro, {c,sr lrcorpl). rt sho,€d u.v.mxlm (6rcobol) 6t t36 n4 (E,sooc) rts irrrd€ar sipct!6
-952.14
--&6.3t6.44
6.42
'41.4?
eae ch€cked b9 lhln hye! dEdcrosr.phy.T!!e q!@!Etl n an6ly6is qale the follovln
{stq.4) sho!€d .b6o!pt1on Fik! .t 3610 (oB)/ 3540 (Ol),3400
(hydlo:q'I), 29s0, r6to (cdbonyl gfoup) / 1640 (un6atutBtion),
l3oo, 1180/ 1O?5, !t0,370, ??C, 6aOCn
cblracterlsatiob o! Ure{eoor.Th" te.te 65 5h4n in tlble ? uele p€!!o!red.
L}-!--!--E.:L
2.
3. 2.4-diiltro phe.yl
a. lod.blcdbonate
5. aydroxandc .c1d
6. lll€def-C!6!ts.
Eulphsi,c &1d.a. iot.l*fraagoatc9. Brql1re 1a acetlc
lJ.aehunq 8olut1otr.
ll.T.lptunyf tetrarol-
11.;erlodic !.id,
rheoolic or enolic
eno1lc o! alcoholic
cdbootl group absent.
cdbo:q|] qroup absent.
un6atu.tion -)rese t.un5!turatlon Pres€nl.leducing gloup ab€ent.
reductng glouP at ent.
tt t6 a cebohydlareor 1ts defivall'v€.i! @nta1n5 adlacent
cH3co gloup lbse.tno qns.tr.tcd lac-
-52-
2.
6olubl€. irlrer, ttrldlne, €thyt alcohol lnd @th4ol.rputnorv $luble. Acetore/ ethyl ac€t.t€,Iaso]JbIe. Eeozede/ chloloform, Lthe!, IEt.erhe! andorner .ontlol4 @l,vents.
tetlllacetat€:- Acetlc lnhydrld€ (5 hI)paa Edd€d to lj,h€.lenol (c,5 cn) dislved ln lyrldine t2 mr)
lnd heated od rate! bstb for tls€e has6. !!hr! arcohol e@aald€d to lhe slurion to destloy exce66 o! !.€tlc 6nhydrid€.the &Iv€nt undlr !€duced pre!s(L. rt yas !€d!-ssorved 1n ettyl .lcohot 6nd ag.lo d!1ed. The regldqe usdlrsolved 1r dcorbl? ard aftef decol,oriratlon r!€ cry6t.t1-lsed f.ofr alcohor-r6te! h.p. 136-3aoc, ,oqnd c,s3.O3i H,5,s4and o,40,33r c25H34ul4 r€qqireE C,53.?6, fl, 6.ur, o?40rt5.It had infr{ed bBtrds at !OOO, r?60, l?25, 16501 1432, t3?0,1260,1210r 1o8o, 960. sd ?65d-l (r19 . b)
ret!. ben4ate derlv.tiver- rrineeenor (o.2 qB), b€nzoylchtolide (3 rI) ed 5J, iDt.hydlo&ide (25 nr) {er€ Ehaken
togethe! visorosly. r, littt€ tu!. o! \oH eolutio. u6s .daled
a.
1r!) so.IubitLrv:-
tlll the !€actlon h1xtse turn€d sltsl,lne. on sh.king, .5o11il 3€ttled .t the bottd rhich y.B c!yst6t116ed lrd
h.p. llt-li c. Fodod c,66.a4, n? 5.1e ,o,2a.1c45E{2or4!€qu1!es c,67.3gt h.5.2. o? 2?,a, rt shored abso!-ptl.on;Eaks j,n tbe htra r€d sFct!6.t 31oo,2soo,1a2o,1750, L720, 7625, 1620, 7175, t30ot 1220, rr75, tooo,935,gI2, 7.1O, aad 6aoc_'-rled.atlop of 3:5_di41!ro rEn66t€:_renor (or5 th) tn lgildin€ uo m]) 3nd
chlorid€ (2.3 gEtre!. be.td or6terThe aorutror r.a rh€n c@i6d anat tDued into dttor€ htd-
!oc!)lo!ic ncldr rhe lqu€ous elutlon uas dec.hred off .ndtne le8ldqe eucce6slvely {sbed rith d1l,ule.sod.bl,cubooar€and v!te!. It rs dlssolved lD .tcohol a.d cly3t.ltt6ed ,!onalcohol-b6o.o!. e-D. 156-58oc.
',lnea.cnol (or1 !Et) r|as d1s6olved 1! minlmlrlr
quadtlty of rater. 6nd to 1t rae added 6 sorutlon o! senUc!_!baz1<te hydlo chtorj.d€ (J.l 9.) lnd sodlh aceete (o.2 erd)ln Ntnlnq quetlt, o! u.t€!r the nlrture rls beoted o, uaterb.th !o! tht rry ninut€s .Dd c@ted. rio. cry6t.rs .ppededev€n on k€eplng uF to thre€ day6.
1th chrods tlro8ld(._ 10 Irn€eenol (5
a slqtion o! llD€._3:s-dlaitro benzoyl
b.th fo! ptre hou,
Attadbt€d *csratloo of sdlcd}Jazod€l
oddati,od of 11neeercr.
or clol (6 9M, tn dtt. H2$4 r6s .dd€d
-54-
lDltj,ore.lhe !e.ct1on hir(tc€ uas left deldght at roon
temrEr.ts€. rhe exc€33 o! cro3 xa5 d€dtroyed vlth netha.ol.lhe &Iution uaa €xtlacr€d several ttme6 |1th eth€!. fhe@r|e! ,a6 lqFved !!6 the solutlor dd thetesldue cry6tal,I-16ed frm chloroton-Ft.ethe! i6o-scoc) m.p.12o-r2ioc. onr€crt6t.lt13ltlon it gav€ needles, m.p. 124_25oc.
ahe lnarared o! th€ product r@ tto.t1ca1 vlththrt of .ntlch.!€noL. The o1&d h.p. 3hored do abpr€sslon.The hlEd m.p. o! its acetare (105-6oc) riEd rlth th€ acetateo! uttcb!!€nol at6o .hoKd D il€pres61on. rhls contlrredth.t th€ oxtii.tion troduct vas &tlch&enol.
!n.md$te. ror.pem.nq6nat€ (2 gns, dtb_Eolved in dlluteil rulphuitc .cld (25 nl) rae sdded !o l1r€-.!€nol (1 th) dlselved 1n rat€. (15 nI, t1u rhe colou! o!tne lEm6nqan6to pe!61sted. It ras t€ft at !06 tqtElatureEor trc daysr \&gne6e dioddc *6s dls6oivod brr thc adilltlono! &dls @t! blsulphlre dd the mlxtule eFllcted vlthchlolofolm eeveral ttheE, ,Ihe chtolofoln 6olution {e itrleitove! lod.sulphat€, co4ccntlated .nd pcllled by pae.lDg ttr_oqgh . col6n ot alqllD. vlth chrorolom .6 trE &1veot. Ih€chrolotolh solution rss concent.€ted and c@-red ,h€n a cd_ired h€Itl.g 6t 196--J3oC a€rlrat€d. tt5 r.R.etEtlm Bhoredbdnds at 3500, 2,0o, t?40. 1260, ed ?20@-r LriBr iUEc). Tf€cwtDurd ra5 very ehBll ln qu&t1ty so fqrne! Flk couldlot rte qde!t!h!D.
IivdEorv6ls 0! Ilne.renol.{j,, rrith soitls hedroxtd€i- llnealeDol (1 9E) xas it1!el-ved in 10.2 ..cr-ht3!orid. (ro n]) dd h€lr€d o! rater blrh!d one hos. th. rilxtse ras €xtractd rith ethe! Hhlch
on ev.polatloD geve no !€sldue, It uas acldlfied rlth d1Lute
ltcl 6Dd agaia eatr.ct€d rlth ether but ao le6idqe xa. obts-1t€d on evilDr€ti.ng th€ .olvent. tbe solutton ra8 ther dliqiund€! Eeduced preBsure ud the reEidue dtBsolved i,n eth!'lal@lDt to !e@ve aodi6 chlo!1tl€. Th€ .lcobol r.s *ltDrated3nd the re6ldue cly€t.lu€€d fld ethyl 61cot61-aceton€ at!d tempelatre 14to a rtdte cdtpuDd .ft€. 3i! ho65. Thla
*As feclyst.lu6ed llnilllly to 91ve pue! product^.p. l,!5-2oooc. The 1.f!ared o: the product shored IF.ls !t 3350,
241C. 1603, t525, 15t0? 1380, 1060, 940, 9!0, e?0. a5O ed
tne hydlolyaed ploduct ra8 ac€tylated rlth lcetlc.nhyd!1d€-rry!1dlne by h€6t1ns on {a!er b6th fo! folry !j.v€
Rrdutea. The acet6te vas lecrystallls€d fr@ ethyl .lco-16] into flde ne€dleE meltrng !t163-65oc. r!6 tnllseit stFc-tra shored F.'€ at 3100, 2t00, r7t0, r69c, 1520, r4CO,
1350, 1260, 1225, llJO? lO2O? e55? ae5, A55,825, ?rO,6nd?3Od_1. Its cmbustlotr 6na]y61. slqeit c,52.24: H,t'.tBt
0,41.5e.(11) 8vd.ol,"dte ulth 2r fi2!9rl!:
llneuenol (t.Er) .nd 2N 6ufphqlc .ctd (50 ml)
e€re samed on a rat6r blth fo! one bou. Thele r6a no
evolutlon of calboo dlo)dd! 1lk€ lntlch!!€not but . b1€d<
aubetdc€ settled atoun rhlch D6s .Ussolved l. chllofoln,dll€d ovo. sd' s91ph!te? codc€dt!.t€d &d c@1ed hot d|1d
not crtf8tllt13e. It slFs€d lnflu€{ teds ar 3soo, 3COo?2aOO,
l?20, 1665, r,i40, 13?5, 1290, lJsO, a4om-r (thin a1lm),
Floo the !qu€o$ $lution, $ t.o!,atea tt ulatt€thoil ahj.ch rd Ld.oti6i,€d .. th. qtu@sazone. thln I.y€!cracEtography alFr€d tr to b€ . stDgle ccqb6d.Aedqcqlon of tlne!!€rcr: -
-56-
@1nj.e fwdrldc. lJlt!l|! !r.@rnr|e" hgal,
rlaL (3,5 sd.r.! alit€a: tolltd€rliaot (o.5 On) in €the!(50 d) .od relt ued or a {ate! b.th dth stlr!1rs lor atxnossr Th6 contehta terG c@l€d lrd .keE5 o! I1thlq .IM-ldr@ hydrid! {a5 il€stloyed rlth . fe{ dropB o! !!t€!r Etheruaa f1lt€..ii rhich left @ resldue on ev.tDrstlon. TiE !ec_tr.or mlxture n65 then diqclted slth ethyl acerat€Fnd the&Ivent d!16d @€! scdlh sutphdt€ (anhydr6us,. the &1u_tlon {66 codcentlated Md c@Ied rhen needtes h.p. 181_a2oc
6etE.ted, shlch Erel$€dtrfte.t .s that o! Ilde{€.o1.111 dlth sodj,q tplohvdllde i - sodt6 borohyd!1d. (3.5 qtu)
voa added 1n 6ms11 !Drt1on6 to lrnegrenor (o.s gh) dlsslv€dln 8Oi of ethyl alcolFl (30 irt). the snrent. Ele t.ft !rr@m r4!E!atu!e !o! trenty tou! houla, th€ &lutlob v.. aci-dMetl rlth i[t hydlehlorlc 6cld. di],uted rtth,.t€! (10 DI]
dd €th.nol ev.!o!rted. Th€ oj.xtule es sats6t€d rlth aod.
chlorid€ and cxtracted ulth €thyl acet.te. The 6olv€.t s!5drl€d over 5odiun buiplate, con.rntlat€d ad c@l€d {he^ ak![le @mpound 6etrElt6 eh,ich nllted .t ll6-1aoc. It st5ved
6b3olpt1on b.od8 ar 3300? 225or l5co, t4ao (Bro.d) 1225,
12Oo 4d Aascm-' tkb! drsc) rn the tntlued sFctrw.att@oted hvd!@e6t100 0f
Lln€*ero] (r 9l , ethyl alcotDl (50 mI) ad th€
clt.IyBt (C.5 qh) uEe stllr€d ulth hBsn€tlc .t!!rer .nd
hydlogei sae !$ all,ored to tldg lnto 1t frd a cyllnd€!.about 50 frI of thc gas rere con6uh€d ln the filst 30 nlnutea
an.t after-{alds ttEre v6a no a!.orptlon ot gas upto th!6€
tecs. the green aolation ra codcent.ated &d p.ss€d through
6 col@ ol aLsdr. vlth €thyl ac€tate as tlE eluen!. lheaolvat ros .onc€ntlsted and c@led rhlch qav€ tbe o!191oal
cdtDurd, m.p. 1a0-182-C,
H€lllnd of Iln€*€pol aLove its meltlno Elntr-lln€{€nor (2 $ns) *as beAted on a 6sd b.th
at 25OoC 6r IO rn1lutes rhen s 9o6 evo].ved. The qa6 r.r lde-nttfied os c.rlbn dioxid(. Th€ he.tl.g sas contlnued tlllthc evolutioD o! th€ gas ceascd. The reEldue Fs dls$Iv€din ethyl alcohoL, d.coloEl.€d vlth !n1mf chrrNll .rd tlE6otv€.t dalo$tedi th€ !.3idu€ ,as d16elved !n tEt b€nretre
ud cooled at !06 tenrE!.tu!€i sde c!y6t.1a sepaEted !!t€r.lDut llfteen daya ,hlch*!€ *.8h€d {lth chlorololn .!*l
-54-
fllt€red. TlGy @Ited €t 165-60 c. IL6 1nalded Blf,ctrm6hor€il t!.k6 at 3120?2t00? 1625, 1550, 13?5r 132J, 1175,
r12O? lO?5/ 1040, 960, 915 €nd ?45cm-1 {}.Er pellet). Du€
to iosqlfj,clent quantlty fath€! rclk euld rct bc codtlDu€d.
;'tt4tt6d re$v1atto. o! ]ln€.lenol *ith diazoctbee:-Itnee€.ol (o.5 9m) {s di.6olv€d 1n methyl
alcohol lnd €rc€rs of etb€leal slution of dlazdmrhde r.s.dded to 1t. fhe leactlon nlrtre {aa left at r@F td!€!!t-qc pvetnlght and then dlI€d und6! rcduc.d p!€6eure. Th6
leetdue {!a cryat.ll,l5ed fld ethyl ac€tEte ed s.s tdcntl-fled .s the ollgln.l conrEund m,p. 180-192oc.
,itt4pt€d @thwl6tlon of lln€6r€oo1 nlth methvl todid.:-To une.leno1 (0.5 sn) dlselv€d io acetore ftth-
yliodlde (2o n1) Bnd !Dt. carbonate (r .lh) {€r€ added and
lhe cot€ats ee!€ leflq€d on ,at€r b6th for !1ve hoas vh1lc6atd1ng n€tht! lodid. at 1nt€rve]s. Ihe reaction mirtce re6
fj.lteled concehtr.ted dil the product crysta]ll6cd l!o!,ocet-one-Fet.ctnlr (ju-iJ-L) n.p. I-J-a2 u, rr ulJ id!nLra!ed sthc orlgln.I c6tDund.
ln"hltlq hvdrolv8i,s of litre.r€oor: -lll:j€luatlon o! trulslon: - ThL sklng *L!e !@ved f!d,aboot fllleen 6r€et almids !V &akIng th€n in tblting raterfor 0!6 ni.nute. the 6lmnd6 rele then ll.ely glound 1n a
EFt& dd miEd to a p.st€ eith 40 cc of sate!, ten t=rc€rtacetic 6c1d (10 c.c) E6 added !o coasulate plote1n present
-59-
and tb. hixtur. allor.d to 6l!nd lor 15-2C RinuteB !1th8tlfflng 3t tntelvafa, In€oldble n6te!i3l sa. !€@ved tAf
flJ,t6r.tton 8nd the re6ldd! ra.hld el'th I les c.c, oa {eter.tlr..dt€.. Eolotlon $6 u!€il for the reactloi.(111 ivdro1v.1s.
l\c linear€nol (0.2 sn), the aulslor &IqtloD(lo c?c) preiEed as .bw€. 16r added. The tta6k rls pleedtn s Hat.!-bathr {ho6t t€rd!€rltc€ w6B darn.arncd .t 45oC,
tor tuo bor6' Tbe hlxtqr€ u.s lh.keo vetl flm tlre to t1me.
The r€actlon m1*tue ,as then e*t!&!€d vlth chl,olofoln 3-4
tiftee, dlled qe! 6od. Bulph.te, th€ eolv€ht !s@€d lnit the
restduc crrltlllleBi !16 be^r6n€ lnto needl€s h.F. r22-23oc.
It ,a ldeatlficd as .dtlch..6rol, tt' frlxed n.p. *1th trElqthentlc aeple. lbd 1n!!aed sFctlq,laol.tlod ol .nt1ct6!ol t -
th€ dry alcoh.ltc cxtract of the pL.n! s$ !e!l-ux€d vlth pet.€the! (6c-go-c) !ev6.at tlres oir vat€! bath.
The rolvedt {€a4g$veil 6dd tlE !€6ldue ua6 di8solv€d 1. !smdl quantj.ty ol rrnze.e ad chlmatoq!.ptEd de! llqnlDsrlth b€nzene as th. elvdt. rrlctlo!6 ot 100 nl elch {er€coll€ct€d eat the l..t lractloda (el€Enth tlactlod oNEds)
on coic€nrlatinq anc c6lrnq gav( .ottchllol h.p. 2-2-55oc.
It 136 lecrystalllred fron hot chloroform into s poed.r rer-tlag at 2-r6-'rsoc (de..) ttr {n!.ced q!c!!@ llros€d potihi
'at !500,3020. 1460, r3?O? lt6o, 1060, rO2O. ?a5, qii ?lsq-lO19,?).
-50-
Th€ lEoduct rd rct fr€€ly aoluble In sy Bolvent
aDd ras onry spaiogly soluble ln chlofofon. €thyl lcetat€
Gtheol, ed cthyl .Icohol .nd 1D6oIub.L€ 1n p€t ether (60-60o)
b€.En€ .nd r.te!,Ac€trl dellvatlv€ ol &tlchdolt- lhe <sFo6d (0.05 qd
f. iryr1d1ne (2 nI) .nd ac6t1c €ahyd.l,d€ (2 nl) r.B horted
oo e6te! blth tlU . cled 6olutlon {ca obt€1.6d (15-20 mln-
qtes.) It ras ther c@l€d aDd llured loto 1c€ u.t€r. lh€
aqdsol1d nEa scIEAted vhlch ,ac succeeslvely raahed ulthsodJclcelollte/bolutlon, dtlut€ h'drochlorlc acld ard rater.It ,!6 tt€n dl,arolved ln nethanol? tle.ted pith 6.1@l ctE!-sal, colcentfrt€d lnd !€cryEtallls€d fron relha.ol-rltertrice ioto ! ,hL!€ rDde!, n.p. 15?-59oc. It 6hopcd !E.*sot 1672. r,i?O, L37at t2fi, 722At 1160, 1060, 1030/ ?85, and
?20@_1 Ir tho rnf!..ed !e91o. (49.4). lts cffbustion 4!f-y3!3 Bhored c,68.9or H,e.46r o!21.64.
Iel6t1on o! frannltol!- The r.aj,due 4, obt6he.l Bfter r6fr-sing th€ dry a1@ho11. ext. o! the pl4t rlth E t. ethe!,
chlorofo!fr sat €thyl &et.te, xe dlr.olv€d lh .leoh.l, dedo-
tou!16ed 6nat co.ceDtrated. Benzene r.a add€d to Elight tqb-idlty &d codtents k€pt iD @1al stor.ge rben clt d.y tMltol.etsated. It r$ recly6tautserl a!4 6fcolbl rh€n lt n€ft6d
at 163-65 C. (375 qM., O.75b). The yleld thpldcd to r,.^
-51-
lhen the plant {ad dh€ctly ortracted vlth rater, Itd 1n!!-a!€dFave p€aks 6! 3400.2950, r45o, rx75, 1270, !075, LO2O,
925, 8?5 6nd S6Oq_1 lrujot mul!). rt 16 1n5oluble Io b€!z4echlorofoft, ethe!, lEt.eth€r €nd €thy1 acetlte sd {aB freelt.ol,ubl,€ iD *at{ .nd ethyl alcohol.
erepa!6tlon or nea-.cetate'- ;..Dltol (c.5 9n)/ acetlc
6nhydr1d. (rO h1) dd fuseit aod. ac€t6t€ (1 9n) {ere h€ated
on u.t€! tqth lor tF hou!6, aDd lbuled into ice. Th€ Eofld
v6r r88hed d.th vate! !4d lecryet6lllsed !r@ 61cohol, ft.p,
722-244c, atx.A h.p. {1th.utbentlc 6eple shou€d no d€p!e-
'!€Dgatlop ol beE-bonzort.:- lb naDltol (O.5 q!) lntyridlnc (5 Rt), b€-1zqfl chrorld. (8 ml.) sa6 added ttr 6!El1
IDrtions ulth @11n9. fhe cont€nts r€le lefluxed otaater
bath for on hosr Iff€d lnto vat€! aod c@led shen th€ &l1daepaE6ted rhich {as rasbed 6ucc.ss1v€ty rith dll.hydrochlorlcacldr sod-bicalbomt€ solqtlon aod ,ate!. It sa8 cryat.ll-16ed !!6 a.I@hol n.p. li?-4:oc. fhe ndred m.p. slth hexs-
b€Dzoatc of pc€ Foaltol shov€<l no d.p.ess1on.
Iaolotton of trlaconr4€!- The Fr.nt, tlJ kg) afre! cold
e)Gr&tlon eilh ,-O- sthyl dcohol (reslduc 6) raE h€ated und.!
lealqx vlth b€ozene on rat€r b.th for ttEee hou.. ln€zen€
rle lecovered .nd the leElduo {aB puritled rrt p.E81ng thloughq collM o! alqha {tth beh4ne as the &lv@r. rhe 61uate6
-62
r€le coicentratea .nd c6led xhen shini.q P1ate6 oa trlacoa-
ts6 (12 qre.0.12',) h.p. 66-67oc E€palated, Its i.trar€dsFctlm slb{ed ab€orDtior 6t 2950, 1465r?30 atd ?lgd_lehlch 15 chalact€ll6tlc of 5n atiphatic satGa:ed hydlocd-
bon. thle rsa confimed t!' the follo:jlrq te6tE!-
lrea lncluAton cobEu.d, the sub5tarce (c.5 qfr) and ur6a
(0,5 ss) vele dis&lred 1r bdtr'ldcohor (!o n) bv heating
on ueter bdth. The clce! solutio. sas left et loon t€r;i6!a-
tGe {he! th€ needles o.f the corntlex jeperated- They {e!e
r€clystalllsed agaln flon tlre 64e solveni d.p' 133-35oC
(llt€ratue 132oc). roqd c,a5.21, d,15.OC calculated fo!Caori62: c,Ai.30; rt,14.69.
Test I ob664at1on
r. !655E19n€'5 t€8t
D1I.raii1o4 3olutlon
It fo.ded a !req-Inc].ualos cdtDund.
-63-
asolatlop of lh€.rol: - rne ratd lBotubl6 Fluo4 (!6si-ilue 2) oa th€ 6lcotFuc extlact of th. !1aot x.. dlssolvdln be.Fn6 .id flltered. th€ ftlt+lt€ ras @ac.ntfat€d .nd
D.8!€d thlougb alornlD. @lum uith L€nzen€ a the slv€Dt.the lirEt llactloft (lbout 800 nr), oa corceDt!.ting anil
c@I''Dg gav€ no clylt.lude plodet upto tEDty dat3. oDly
! c16! oolllr e!. r!! obtatrcd rhlch d16r1U€d 6t l4Algoclo.2 M. It ra6 cryst.Ill!€d frd b€nz€ne n,p, 2l2l4oc. rts.Fctrs rlbred F.k .t 3500, 3000,1t50, 1700, t65o, t45or
13t5, t2OO, 1060, IO4O,91O, lnd 9?06_l (F g. 9) so6itc,52.89r ri,6.a2, o,40.29; cl6 H2goto!€quues c.5t.33, H,?,15,
o,39.sl.
rc€tvl dorlv{t1v€ of l1n€eolt - r,o th€ cqrtbudit (atbout 0.2 9h)
d13&1v€d li tryrtiltn. {2 nn), &€tlc 64}ryit!1d€ (2 nr) e!. added
.nal th€ 6nte.ta harted on r.ter bath tor tF lDqla. atto!c@l1ng tb€ leactlon nlxtu€ ras tbsed lnto 1ce-xstei. rhe
lolid 9roAuct ra. th€r ftltered o! and ra.heal luccesslv€Itxlth illlut€ .od. btcalbon.te aolutlon, d11. hydrehro.tc lclil6nd x6ter. It r.r r6c!t!t.ll1a€al flor cttFtrol-rater to .cdsist h.p. 124-26oc. the 1n!!e6at .IEc-t!6 EhoGd b..il.!t 3OOO, l?40, 1?OO, 1640, 1360, r250, (should6r), 1210,
loto, 1040, 9ro .nit a?oo-r (F1s.lo) loud c,54.26r H,6.44,
O, 39.30, C--H--O-- !.au.l!e. Cr54.24, H,6.56r O,39.ra
Ielatlo ot B bt&k lcidr- the beDr€De lEoruble restd&
of the ,Ete! lEoIubI€ trDrtlon {lrq lj,nesol) rll il1.&Ie.a
t^ cblolofolE .rd flltd€it to ! cl€lr 6olutlon.chlorololne!. rmv€d eal th€ lealdu€ drl€d cqnptetely under tEus.rt i.a th€n iBa&lved la dtl.r<d.htdrorod€ dd ftltcr€dl. lh€
!!lt-!.te '4 &idla1€d elth iul.hydrehlorrc .ctd rb€. th.il.!k t!€ctpttat€ .ettl€d ilo6 rblch fll rahd tholoughly
rith r!t€! .nal (lrI€al. It ra. €lut€d throuth a col'r$ o! 6lq-
olna rlth chlorololD A! th. .ol,v€nt. l'ho cdltbund got ld&rb€dl
oD the .lohln! and therelor€ ra3 €lqt€d ,1!h .thyltc€tlt€ odther mthqnol. lh€ €tlryl .c€t.te t!.ctlon a6ve no !€rldu€ o!
4.F.!tlng the lolv€nt. lh€ mthyl al@tDl solutlon 16.
coE€Dt..ted .nd [email protected] blt no cry!t!I3.aet$l.t.d q)to t€n
d.y.. EtrEr rs ldd€n !o thl. tolqt1otr rheb tlE !.1d .clE.ted.tt e!! r.sh€d aDd then d!1€(1, lhe .cld illat not mlt ugto 36o9c.
It r.. solubl€ ln ,ate!, dll.lodls htdlodile itllut€ !€dim
btc.!bo..te solutior .Dd €thyl .Icob.l. dd ,as lFrlnglv aolubl€
to rethllol, 6nil other o!9u1. tolventa.
rslatton of Flunedolr- After the llolatiotr o! lln€.!ol'lho colum ras 61ut€d rlth chlololorn. lhe 6olv€nt
t!.tGd .nd c61€d. No cry.t.llln€ lrodqct &Islt€d otto .fo.ttrlght. llotr.ver, lt ru Fr€clFltated t'| the lalill:lar of
rFt.6th€r (5O-?O'c). lt rat .g!tn Pu!Med by tt..lng thro-
ugh . colle oi 6lu4le (E.!{€!ik) dth chlodfom.! th€ rolv-
ent. It r@ @rcentlAt€d lnd the lsodqct crlEtlllls€d tron BGn_
@rF . sthe!. It nett€d !t lt6-19'c .nd 1t5 1.R.tl)€c!!q
-55-
(Flq,2) Bhored p€.ks at 3500,2900,1.720,1640, ( should€r) , 1440,
1360, 1225, antl lotom--.
@atter the lercval of n6$ltol le6tdu€ 5 ,€s d1.._
olv6d 1n dj,l..Icohol and slotled on shatnBntr ItaF No.1 along
rith the st-t6 of suthentlc a ples ot glucGe? lluctoelheros€, ma$1tol,snlactose, Eltose, anil sorbo6e. The chleffitoqr6h {sE lun !o! Eeveoty fou. tpq!6 Ptth the olgelct.yd o! but&ol, acctlc acldr uatlt (4t1t5:). lho chr@ato-
sre rE dlled ed sp!6yed lith aqu@@ 1,| stlve! Dltrat€
6olut1o. ln 6cetone, dr1€d aDd then stE6ved elth .queo!6 2h
sbdt6 htlroxld€ soJqtlo! ln ethyl al,coho1. otrly thloe Bpoltt
coqld be obs€n€d od drr'1ng the chr@toqrd corr€tlprillrE
to glucoee, FannoEe &d (6nn1tol,.
-56-
!b. l rc.a .tEctr. .t t!. c-F!I. atbcrhdituo rrtt-cb.at. ll!.$t. .!. o toltn.r-
0r | 6 a f t 0 0 ll ll E t I
on
a
rso tlo tlo m 6+l u o !0 D
0
mnuiEriot- (O1cl3 !o[)
Fig. 2
I
folrl"Irl!Jrl
-[rol
't!fol,t
1L
.47-
!@ r& r{r! r,rxrouff$( (hjc r.o)
Fig. ttaf
N10 ls 19
uia &lo! (rrjd t{d)Fig.4
{, l,
t,Iata,II
W
a I nt6ll'1.
I'lr
lrt,J;I
a
a
I
tD
!
t,
lr
-68-
ts
,atot|rfAficratlr€! rEt ll (t},
F|9.5
uiaaaro! &€t t€ (i|. .!a)F19.6
lc
@1@
-69-
arl!ollArTlGHrt0! (Mrjol Y.lo
fig.7
r!6 cl}l
arSrollAr{TtcfiAno! actTArE (ngjor tdl)
ri9.8
r1@
ll
I
l.,
0
aroa yt@
4
so
-?o-
a00 & t60 to (ta{ go t4 0o tp
!|.
5
D
0 n ItattttnrricAt0r (crcrr $r-)
ng9
rg clr
lrttonune^io! ActraaE (c{cL, 5ol)
Flg. l0
re,ol0
,
o
!
l0
o
caBtrcAL INVISrI Gi{t Oil OF
].lJTICtt RTS ClJ"tiUJt OSra J,SCHERS.
fh( plst dtrch6rr6 gl&dulosr grds in Lhe !ocl<t'
aleaa rn th€ viclDlty o! r@t!1, dd fb6nobul. Khd (Dj,st.Dadu)
io the foner ploviDce of Sind. Ir ts also .vslIabl,e ih theplalns of Jeelero mstfy 6lound ttE utrlverstty cdpqs. M,sreFlted to b€ scatt€red tn slmlld envlrorments ln Khotlpur
div161on dl6o. It b€fongs to the feity scrophurdiaceae and
1s itaelf d aeual vlscid h€lb Htth glaDduto!.Dd lEily lcov(s.It i6 $ucUy .e!1l6ble after the some! r61nl.lt ad r€sche6
the fto*rlDg and fruit folmatlon srag€ du!1.9 Octob!!-nov.nbcr.It. hlxlnuo hei,ght d@s hot exce6d 9-10 :ncrcs,
Tb. plet la rDpul€llly kno6dd 1a uB.d a5 a c@e for dlab.teB rel1ltus ln tndl_gilous
m€d1cin€. It lo.c .brDdotly rhen srskea rtth {ataa ad iEthelefole often used bir Iocor6 6s s sqbsrltute tor 6oap for{ashlnq clothea and cotton fab!1cE.
Aa no prevlous rolk has beeo leFolted in l1t€rat-qe on the ch€hlc.l lnvelt1getlon of th15 pllnt 1t ,as .orsl,-it.led appropliate to 16ol.te th. active pr1lctpl€6 present rntlr€ pl,ant and fulthe! to 6tudy th.t! chemlcd satule ed ph.r-Mcologlcal propertles ln thc hoF to se!.ch stu ns or6t]y.
active &tLd1..!Et1c illut. lt $a dao thought to De 1Dt6ea-
tthg to corltE. ord If tDrlibl€ cor€Ilt€ th€ r.!ult. obt.ln.al
rlth tho6e of thc othe: plant ]stlchall! tlre.rl!.lhe lollalnr lchd'€ (t$l€ -9 ) t|ls !d.!t€d fo!
the 15ol.t1on ol tht .ctiv. tEliFipl...L4--l-14-I--:--4
BeEene .oI. pl.ht r$tdu€.Ees!!1!gg$se-
othYl'dcobl
(dr!€d)
i€tbyl6c€t.telentth@ntd€
extlact .qu@ur !ol.sl!4cgl9c!89.'l.cldltlrd)
'€tlryl,6c.t!to,
extr6ct rqu6o$ lol !c16rdu1o61c rc1d. !!!!89.!.
-?3-
.. !'1s.1t /_1rrc),611- gI.Adulo6a,*c,{rs.,rd6:0ro .r ) rrj rrL uilv(rsrr, cqpJsttr( @ntn o! octob.r,
Tbe benrene ext!.ct 9t th€ Pllnt on concenlrlthg
.nd pu1!y1ng thlough . colum of .loot6 ttelil6d e lllttrt1chtid!@a!!on m.p. 6?-5aoc xhlch vE also obt.lhed frd th€ hot
alcolDllc extlact ot tb€ plst. It o.Iys€d !o. ca1lk4 lnd
lorEil . sea adduct n.p. l3l,-32oc. rt! tnfllr€al BiEttutn v@
Eh1le to that of ! Eaturlted bydloclrbon. rt ra8 1d€ntllted
!3 s4trllcontde t{' ftlreil rlting rbtnt rith the authorttc
s.nde of the hydrocebon.
The u.te! 6olqble lbltlon of tb€ dlled slcohou c
ext!.ct of th€ pl6nt !ee1d@ tro aboee gd€,o shaktng rltl!.thytlc<tate,a ,hlto c.ystllllne ploiluct m.P. 133-35oc tenta-
tivelt cllled as Glaoilulolldc- It 6n.I}E€d lor ca6l62o15. lhe
!qu@s lolutron on actiltflc.tloh q.ve 4 acrd fr.p. 194-l95oc
t€nt6tlv61y c.lled Bs 9L6Ddulo6lc .cld, It e.lya€d lor C2?
lra6ol2 and coulil !l.o be obtaln€d on .Ikdl.. btltoly3l! of
glddul,o.tde. Both gl.Dilqlolld€ ed glsihrldlc 6cld q)iEs
to be !4 conpourd6 stnc€ th€1! pioP€lttes 6Dd Pr'y€lcat ch.r-
actelistlcs alid not colE*e vtth dy ol th6€ cqqFud. atee_
libed tD th. llt€!.tr€ ,ith lqe rcIecu]'s cohF.llt1oD.
the .queou€ lolutton lrd abov€ on conceotratlng
anal c€ung qave . needte ttk€ cry6t.Itln€ Fodqct Gp. 163- '
-64pe rhlcn folmd .n ac€tlte r.p. 122-24qc .nd . benzo.!.
h.p. 14?-14e%. It sas 1il€ntMed 6. Ednltot. Be.ld€s n€ft_
1tol,glu@s€ 6trd |t|!Imse rcle arso Ir€eot tn th€ &lu@u!
aolutloD .3 tlE trc sugatav€ o6@onea ,ftr sugarE rere
,r'y irate! ch!frero"lophy dd 1dentM€d.
of Glddulo5ld€ .nd Glsrdulo6lc acld-
c1.ndu1os{d€ foes stlotrgly rh€n .hak€n lD 6queoue _
solutlon yl!,'cb tE a chdact€r3li,c ploFlty of pr.at 6a!or1;:l,il<€ othe! Ealonln6 rt i,s v.!t todc sd ex€lts ! tfterlqlh6doritic elfect ,lpn injecteit 1DtlaFrltonlauy to r.bbltdeven 1n extlere dilutlors. rlth t€treltrdethd€ lt alo€!
tot ij"ve dy colou! @! d@B !t Ehd ary setectlve absorpt-
lon ln the u.Ltraviol6! legion €tDv€ 2ro dlln.[c.tlns rh.t
cdloMd is fully a.turated. The inllu€d atEt!@ of gl.Dd-
u1o61d€ 6boo€d strong bands at 34oocm-l (h!'d!o:qrl) sd l?Icfir(c4tebyl) - It folG an acetate fhlch d@3 rct cry3t.1l1.esd_3:5-dinitro t€nzcte m.p. 114-l15oc. 1t doee rot ho{ev€r.folm a s€ricdb.zooe o! a 2:4-dio1t!o phenyt nydr!2ore rhlchiDdlcltes th.t rt doeE not cortain . f!€ csbonyl group.
Ctaitluloside glves a positlve hydroxeic .cld teat ald !d€gatlve l€gal test {hlch shds th.t 1t 1a a. erte! od not
a l6ctore. It 1s .a31]y reduced !'y lrtblM .rqninl6 byd!1de
to 6 product n.p. 235-23s% xhicb lhoxs no b.nd3 colleFnatlagto cuboDyl group In the intlded alEctrs ol the ml,eul€.iuite concei,vlt'fy the €ste! group - cooR haa been leduced
to 6 -CH2OH group 1n this leactlon,On atkallne hydlolysis gledulo.ld. glve! gl.lalul-
6j,c acid, t,he 1nfr.r€d stEctla of gledtloBid€ and qr.ndulosic
-t6-
!c1d rere slhIls j,ndlcdtl.s the cto.e rel.tionrhlp o! th€fotu! ritti the Iatteri the only aulldece b€lnq th. !tEE!-race o! . nd b..d at l25od-r .nd . 6hltt of the c..bonyll$rd flh l?3od-' to l?106-1. filt. elltft ls Gstry .rbntry the €stels on htrlroly8l. to th€ dlr66l.DdlDg .ciit!. I!1s th€lefole tEob!b1! th.t gl.nttu].osl& ls . BIDDIe €rtorof El&itulo5ic 6cid.
on acld rrydroly8lg both tlsilulGide .d 9llndur-o6j,c .ctd furniBh the sd€ 6qluco-e c2O H!4 oa s.p. 6o-62oc
snd the sa@ sqg6r rhlcb uas td€Dttf1€d thlough tlF rlFilheltlng tFint of th6 os.zone dellvatlveB. Tbe Lnf!l..d ti,ec-t!@ of the 591ucone sho,6d th€ h!dF:.r'l ed trE c.rbnyl,tard trt Dot the e6t€r bantls. rt 1s thllefole coclqit d
th.t the aslucone has tost th16 srour6n e1d hy&oryris.nd it5 neLr€ Is th.r o! . tero alcohol-
The mas. .tr-ctrM o! ql,ddulosld€ 3te€at a iFl€c-ulu ion tpak 6t n/e 444 vhfch ls nedly 3o0 unlts loro!than the one obt.lDed !y o3m6t!1c &d Rast hothoda.Aga!!
thls v.l,ue is con61d€rably lorer th.n tbe e:SEct€il el6c-el.t Glqht of the eatDnlh6- Fnltbe! lt 16 cll ](troh ttul6qge de!1v.:ives 4e frequ.ntly t@ ldolltlfe to gd,v. a
nolecula! io: in the m.ss +Ectru. It 1B tb6lelore @nclu-d€d ttEt the peak at tl\/e 444 1a rcEt l1kelt due to th. Fn-Busa! resldue of rhe mle.ul,e. on the othe! hsd rh! i4!ar*trM of stdduloalc aetd ehd€ . rclecul6! ton F.k .t
m/e 4oo. irhele6e lhe Bolecular r€ltht ob!.ln d tn taltll of
€qulvlI€nt rei.ght 
qiandulo.td€ rnay b€ a c!rd16c glu@ttib !.latd to Ddap&
tr€trrD (36) ior sti."blltDldtr (3?l
tbts 16 quiro tDsstble er.nc6 th€ lo3t 14,ortut gEoul, ot
the cuittEc qlucosldes o6tne dlgttau! h8v. b€on lrol.t.alf!@ the sp€c1e6 ol the scroprndatbcer€ fsilt. Li.vitr -
ttrte h6s not b€ ertsblt.h€d 4 y€t, tEthlt lqk ta tqur_Eed to study th6 gtnrctur€ o! tb€ lgluooo€.
Thc Foltble @o!s6 o! btdrort.ts .t th. ts€|rlcdpoqnd und.r 4tv6nd alkllia€ conilltlorl. €:gldned |l
u.;.?!4 ca6 2ot5
I| *r,JiI
l*tI
Jii.vr.40O (C2lL360?)
-"2o
stod-t€6 o. ttE slltr@tton of ttE !!ov6 6uEa€ otb!'drolyds and the €ttucturd elucidatloh o! gl.ndql,odd. rnd
gllndul@1c acld t. 1n prosr€sE .od dll De !€Frt€d elt€d.rerlpo cqtrI)leted. Th€ preent !€rk ra dly 1nt€dled to l@LtcuE !M€ tEthcrtn€g of the pr,et 1. & €llolt to e€r14' th.leFrteil hlrirqlycenlc actlvlty asaociated rtth tlE. Dctdl€dphrnacologlc6l ltudje6 d€ delcllb€d 1D th€ lolloxlng &ctlc'n.
c27 H46ot2 b.e.r62
II
Hcr
J(c2ln36o?l !r. r.40O
I
| -"o,
I
c2od34o4 !i.ir.338,
r&htron ot cl.ndolosld€r - rhe pra.r &g!.g!r4!_gl!4gr!9!E(2 kE) r6s cut lnto irlsce! sd leftl*d eltb €thyl alcolto!
{95 t) oD r6te. bath th!6€ tlne6 fo! thle€ hourr €ach ti,n€.
th€ alcohol ra! !ec@e!€d lrd the !€eldu€ al!1ed cmplot€Iy.It re dt6Bolved tn r.t6r .rd !1ltered. Th€ futr.t€ r..!'Dx6n utth chlorofon .ntl €thyr lc€tate anal €thyl aq€tat€
.olutlon vls dlteil @6r sod. sulphat€ (abl!dros), 6rc6ntr-
.tod rnd coled vb€n cryst.Ir of sl.nalulo€ld. letElt€at.TtF:_ ':.!. :e.r:.it!tlt6ed lrm 6rhyl 6cer.t6 {6 !N o.3t) to6 co r.nt n.p. 133-i5oc. rh€ ."r'** "*.*liiliitJ"u *robandrst 3420, 2950, 2815t 7730, 1455, IaAO, b?0, lnd goodn-:
Ioed c/58.3r n.A.9r o,32.4, ca6862or5 lequlte. C?5a,a5,
H,8.5; o,32..:5.golutrlUtvr- It ru doluble l! eater?€trttl6lcohol 6Dd
eueot, epcingly 6otubl€ 1n &eton€ sd ethtl. 6c€t.t€t6nd lmolubte 1n rret.eth€t, b€n.€tr€ 6rd oth€! tron-Fol,u
ciBrsglsrq9!t!-s!-9l.nggl9s!d9!-
E_-I_!__E_8_J_-E_E_U-A_-L
It 6s chd6cterl.od ll ildn lq t6bl. 10.
-81-
11) ?unctlorrl gEoup
2. lerric chlorlare.
3. Certc nltrate.
4. 2:4-dlottro phenyl
5. Fllealel -Cralts .5. Fomrtaelle.-:ula
7. Dil.XibO4 solution.
8- Blofrlne {ate!.
9. Iitdro$rnc acitl.
1O.T€lranltro hethane.
nitrog4,allPhq rbd
Dh€noU. or e6ltc
enorlc o! .lcohollc
.*bonyl sroup 6b$nt,
it) colour te8ts: -It tE5 !o ls6trat€d
tt ta . etsold or .
It ts . at€lold o! !
-62-
3.!!e!E!tion of acetvl derlvallve:- clanduloslde {o.2 !tn)
ra6 dissolved ln pyrl.tile (2 hr) dd ocetic &byilrid€ (3 ol).It eas heated o. {ate! bath lor otre hour, cooled ed tDcd1n lce-s.ter. the resldue ra6 rlshed successlvely vith dllrodblcalboEate, dil.bydrochlorlc €cld dd rator. Arr 6ttaptsto clystol]ise tt fld ditfereDt solv€nta !al1€d aod lFte.da gl43y lesldue ras obt61!ed rhlcb r6s tBsa€a thlough !collm ot alurlla ulth ac€tone 6F the Eolv€nt. fhe &l;r|l '
cclc€nlrateti anil c@leil but no c.ystalliDe Ploilet setaatqr.
The pqle past€ gave I.n.trEaks (119.14) at 29oo.1?45 , 1425,
1.]65, 1250, r220, !t?5, 1060, 1025, 905, and ?304-r, 'hich
shd that th€ .cet6t€ (very 6tlong lp6ks at 1?45 .Dd l25o?
4- LreDdetion of benz6te aerlvltive:- clandulosid( {o bE'
12206-1) ha6 actu6lly b€en forred.
?roo-r (chlolofoln solutlon).3:s-dinltro tEnzoat€ derlvatlve,- ehndul@1de
benzoyl chlorld€ {4 mI) ond dirute pt.hydroxide solutlon(25 nr) uere Ghalen viqorolsly, !.re lDt.hyitroEd€ Eor,ras
ailded to rEle the lelctlon dttule alkal1te dil 6g.in the
content6 ahaL€n {hen . 5o1id aa66 settld at the botton. It,aa ,ashed rith di1.!td!@ilo!1c acid 6nd the. rlth rat€r.rt did not crystalllEe frm dy solvent 6nd *aE turMeil tt'tDlltnq sitb aceton. m.p.9r-99clts I.R.Er*trs shdeal bealt
ar 3050,2950, 25609 1?AO, 1600. 1450, 1275, 1175, aOO ud
(0.5 9r)
ea6 dtsEolved 1n dly Fyll,d1be (5 hI) ed to tltlg
-8!-
b€nayl chlollde (o.a sd {.6 .dded ard the .ontat. }E.t€d
on a ,.t€! b.th to! 30 hrnute6. After c@11n9 tn6 aolqtion
ras lbuled lnro duute htdrehlorlc acld ed !11ter€d. It|.soud tEoduct ra6 then succe68tv€1y e.shed sith dlt.eal,btc&honate solutlon 6nil theD dth r.ter. It e6a dla$1v6d
ln ethyl acetote ed drl€d @e! .od. 3ulrtrto (Bthydrou.),
co.cent!.ted ed cri.tallared !!o ethtl acetate4lcolbln.p. llA-2ooc. Found c,48.2r H,3.5: o,34.4, N,9.9, ca9
Iisoo6oNls !equr!4 c.16.6, 1rtr.2, o.3?.9r N,r0.3 lor nln.
neiluctton o! dtddulosld€ rlth lttlr:'s aluhltlu hrdlider-
To sL!.duloside {0.5 qm) in dly eths (50 nU
L1Al,lr4 (r qv {as ld<led lnd the 'ntxtur€ he.ted und6! leflq
fo! th.ee tEss }lth etj,!!1ng. The eth€r solutio. e.! ltlt€r€dthe 6otvert d!1€al ove! sod.sulph.te €nd evaPo!.telilbot notbing
vas obt6.1n€d lrd it. lh€ lesidue r.5 dlasolveil 1n t.eretrDrl .l,corDl, concentllted a.il cool,€d rt€n c!ts!al5 nottlnE
.t 22?-32oc {€!e obt.In€d tbich Er€ !6cryst.1113d frdthe sde sole€nt/ h.p. 23?-3fc. tts lnalared spectruD
lle€d bsnds .t 3450, 32oo (b!o!d taDd), 2950, I5?0, 1450.
l3?0, 990, a9o and 720@-l (nulol ruIl).It. e€ly6ltdl,d not colle6tDnd to the .:qEctetl qlcohol.
svilrolvEl. o€ qLandulo6lde. crandurostd€ (0.5 9s) $al 8od.
hyatloxLil€ s'^ (2o nr) kle dmed oD rat€. bath lor tr hoqrr
c@1€d lnd the contents eltlea od €ltlact€d rith etbylAc.tat.
-44-
seveial t1ne6, d!1ed over soal-sulphlte aDd coDc€otrateal.
A rhlte crlistalline chiDurd r.6 s€pdat€d on cooung {h1ch
nelted at t7o-73uc. It r.s dissolved i! 6thtl .cetate,t!€!t€d {t':\ n!1ha] c}Elcoal ald rec!y6t!111sed to thE
ql.ndu]ciii. icid reltlng poin! lgl-a3oc. it'und C,5?.3rH,a.8
O, 33.9rc2?ti46ot2, requlres q 51.6r H,a.2r O.34.2. It aho{ed
lnfla.ed peak (rlqr12) !t 3490; 1710, 1360. 1o8O,9ooo_r.
]!cld hvdrolvsls:- GlrDculoslde (0.2 9n) aDd 5r hldE4hlollcacld (10 n1) sele h€atea on {ater bath lor flve hou6 xhsa 1j,qr1d d.ttl€d d@a in ttte botton rhlch sllallfled on
c@l!ng. It Naa fifteled sal lec!'stllrised t{1ce fr@ chl,o-
!olom.-pe: .the!, h.p" ao-82oc. losd c,62,?8, 8.e.43,
o,2F.]9; C- H--O- .equi.es C,63.0; H,9.0i O,2a,O-It qBve
r-R,bands .t 3500, 1?oO, l?ao, lo?0, and ?2m_l.1he acetato
d€!1vatj.ve lrapaicd es uBusl hod m.p.tt5-t6oc.!!6 the ..ueous sotution !n os&one F.p.2og-lloc 6eis.td.Itteh.ted eizvmatic hvdrolvsts:- GlaDdufosld€ (0.2 gn) e!5
dis6olv€d i. sate! (s nr) bd .nulsir solutlon (r5 ) (pFc-
edqe.n r:.!3) uere {ah€d i! a rater lFth st 45oc for on€
hou! - rt \i: then 4tracted !j.th ethyl acgtat6 lrd {hlch
tl€ orlqlntl .6,:.@d crystalua€d out on cohcotr.tlng and
c@ljng th€ .o1utlon.
r€thvl.tl.! : qr ar- irlc.rd..
l1)_!!t-!-q9S.rLlsj!i:- ctacqloslde (0.5 qs) lo acetone
(15 s1), mcrbtr 1od1de (r5 hl) and tDt. c4bonate (l.ogh)
-45-
re!€ heated unal€r reflu for fou houts. }b!e @thyl lodtde*as 3itileit dt !€gule 1nterv61.. Afrer c@tlngrrbe soluuonra fj,lt€red ard th. :e51dqe dlgeeted eith acetone trlce,@nc€ntlated drd recrFtaluged !106 .ceton€_lEt.eth€!(40-6ooc) m.p. 1!2-33oc. rt ra. ldentlfied .6 the oltql,Dal
(11)w1th di&m€$ee:- cleduroglde (0.2 Eh) eas aUsaolv€d
In nletblnol (10 nl) ed etheleol dlaz@rhBne ioturlon v6!.iltleit to 1t i,. €Eees. rt {as Ieft 6t r@s t4tEatu€ lorteenty fou! houls durrng *bich a!, azm€thane uas add€d !tlnte*als. the solvert r6s watDrlt€d ude! r6duced pres.ure&d the ploduct recEystaUlsed frm ethyl 6c€tlte [.p. 131-
!2oc. It se6 .lso ttt€ntltted a6 the ortglnar cotntpsd qraad-
the Frant { 2 ks) *!! cutlnto salL pteces and lelluEd {j.th 95t atcohol th!€e t1r!on vate! bith lor foG hou!6 each rtue. TtE li.oohol |'aslec@ered 6nd the €xtlacted sat€!1al dlred cmpl€tely. th€crode extlact (d.rl blwn) ras dl.sorvcd 1o dllute hrdfochl_ori,c acld ed flltercd. r'be !1lr-rate re 6h.k6n succ€6s1vely{1th b€nz€De, ethe! and €thyl 6cetare. ooty ethyl acgtltefractlon on sncentratlng dd c@llng, 96ve ,hlte crystals.Tbeae uele dlesotv€d tn alcohol, d€cororlBed ,tth .dh6lchalcoal concentlated dd c@led but no crystats sep.lateat
5o arcohol {$ coilpleteLy evatplat€d 6nd the reElarue
IBolatloh of dl<,nduto61c 6crd.
.l6-
lecrystalll3ed lrm ethyl .cetat€ thr€e tlnea to Eive 9l6nd-qlostc.cid n.p. la4-65oc (2.5 q6, 0.1!t).Dud c.5?.30t
ll,S.8O; O,33-90, c2it s46gt2 !€qu1!es c,5?,60, A, 4.20,
o,34.2o.lho ftls3 4,p. ,1th tb€ !c1d obt.hed on altaurchydrolyals, cd qlsdul@lCe .hded no d.tretdon.lnf..r6d , .
sF€ctlh 6hd(at bdil, !t 3490, a42O. 2960, 2900. 1?10. 1465,
1380. 1260! IOEO &it gooo-r (Flg. t2)
th6 eI€rcDt tests 16!€ r|<tqtlv6 !o! n1tlogsn,tq1l,hE
The acld *!s aol,uble ln H.t€r, 6thtr dcohol, €tlr!'I
acetlte' ed 5oal.b1cs!o..te 8olutl@. tt ra! lEolubl. 1tr
benz6r6? !Et.6th.!, (6o-aot), eth€!, cltlololom ud illl,hydlehlo!1c &1d.
chu.ct€rl6atton of ol.ndulo6ic acrdt-
The fsctioDd qroqp 4d other t6at3 e de6ctlb.dln table 1,1 ,6re tErfofttt to cha.cterls€ lt.
!-!-.t-!-E -:-Ll
I. F€!!1c chlollde
3. 2:4-d1r!t!o phenyl
4. tbreldehyd€ -lul furlc5, Frlede!-claftt
ph€nouc or onouq
€trollc o! d@lbuc
c&bonyl crouD
6.sod.blcshonate I dl56olved lcalboltfllcqrouPsolutlon. I vlrh €lf4
?.Iot.peln6nghot( | not d.col- lno unEoturatton6olutlon I ort.ed
S.B!6nLne lD .et!c | lot decol- lno un..taatroD6cid I orlsed
9.tetldLtr(rcthde | !o &tou. lao qaartur6tloh
1o.!1.b€!Das-Bqch- | po.1t1ve ltt tDs ! ateroid. ild I lnucl€u..
!o61t1ve llt h.6 6 stdotd
ieelr! de!1vat1ve of d),andulo61c ac1d. the .6po6d (0.1!F)
dls*&ed 1n l)yrldtle ( ad) ras healed rlth acetlc ulitdrltle( znr) lor tb hoss 1n a rtte! bath. Th€ soluti,on tl. c@led
and tDured lnto loe-{ate! {heo . soud setrlated rblch i,.r*ashed succeselvelt slth d1lute eoiti$ blclrbonate €otutlory
d11ute hydlehlolic Bcid ed vate!. lt r$ iu6solved ln.t@ho1, @nc6ntrated and cfl€d. No cryetaUtne troduct
6etEet€d, /;Ll att4pta to r€c!y5t.11136 Ialled. It dor.at
lnf!6red b.ndB.:rlq.l5) at 3400. 2950. 1?50, 1375, l34OIa lrGad bahd) ,10?O oit 10406-1 (c}llolofom solutton) .
3!5-i11.!tro-bgrzoate o! d und
(0.1 sn) rss dis6olved tn dry t)!'rtalne (10 t0l) dd 3t5-i|lel-tlo belzoyl chlo!1de (o.59s) Eddeat to lt. The r1xtur6 !{.!beated 6 {.te! bath !o! one }Ec ed tbured l,.to d1lut6
tydlochfo!1c scld rheh . .oltd Eeraatod ,b1ch va6 !1lte!€al,
-aa-
rash€d vlth soit.blcartotrste solutlon oil then slth vat€r. It'e.s rec.ylrAllised (16 dll,ute a.etoDe, [.p. l4o-l42oc.Itethtl.tLon of ql.-dtrIoal.6ctd eith [email protected]:- t,tle cd-Fultal (0.2 gn) ra8 iU8eleed tn rethyl alcotpl (5 nI) eiletheleal dlozorethse 1n excess ds add€d to lt. rt sas troptat !@m tdpelatre ovelnIght &d then d!16d stic! leduced
Pieaase. It did not c!y6t!ll13e ald ary lol,veDt. lhe qu.n-
tlty r.a very saU so tuthe! rcEl< could not b€ contlnq€d.
Hvdlo1vs16 of dlddulosic acid.
{1) a.ld hvdrolvsis:- clondulosic 6crd 10.2 gi) sal 10i hydlo-ctllollc acld Ele ttcated i.n c retd b6th fo! flve hoss {n€D
a 11qu1d aettled dlD, rhlch sottalMed stEn the contents [email protected] 6queos solutlon xe d€cstGd ed the sottd r.srectyrtllltsed fld chlorotorr Fr.ether (50-?Ooc) m.p.aO-
62oc. It g6.re r.R.b.nda at 3500, 3oOO, l7oo, 147or 13aor 13OO
lO?0, 930, 8?5 and ?206-r(.ujol suU)r rhe lcotat. ':t
rtv.t-j,ve p!ep6!ed in tbe usu61 n re! had n.pll6-1e.c.t!. p!od@t.
ra6 ldentlcll eith the ore oblalDed fld the 6c1d hydroly.lao! ql6rdulo61de. the hlxed s.p. o! tbe ts producb ed th€t:acetate dellrative ehoucd no d€Ire661on.
Th€ aqueoqE Bolutj,oD save lo8lttve uoUBch t6!tlor carbchtdrat€E dd f!6 1t plqEed as usu6J,.
.elErat€d rt[ch had the n.F. 209-11oc . th1. o!4oc $d th6one obtslned tr6 gr{Auloslde on acld hydlory5ls {e!e lden-tlc6l r! ah*n h, h.p. .nd m1red melting loj.nt of !h€ tro ,
l11l itt4pt6d eprrmtlc h.ilrc1v816.- Cileduldtc .cid .
(0.2 9n) va. dl5&lv€d 1r r.te! (5 d) qd dul.ln .olutloa(!5 nl, prelElci eF 'rette) rere x6m€d on o r!t€! bath,
Hhos6 tdtEratu€ r.s s.lnt.lned At 45oc, !o! one bou!. ttrl! then cxtlact€d vlth etbyl acetlt€ frd rhlch the otlg-lDal cqtbsd a.,IEotcn.
[email protected] o! Bnbitol:- TIE .ctallc solqtlon .!t€r the
lsolotl,on of gL6ilqlo6tc lcld rar dlled cnpl€toly udo!reituced p!663u€ ahd dlssolv€d 1D ethyL atcolDl, d€colorl.€d
coDcentr.t al .!td c@Ied 5t !<m tdpe!.tut€ rhen the nedla.o! Mnnltol 8ep.lateal alter tF d6ya. they r€r€ r4lystall-l,.ed !!6 clcohol-b€EeDe? h.p. r62-64oc(?.12 qr.ro.35!t).The lnfle.d sr*tlq r.e esctly stdilu to tbrt o! 'llnnltolAnd trlxed m.p. vlth authqtlc 3sple ol Fnnltol Bhon€al no
olllE carbor.reiife.r :: . Atte! th€ [email protected] the.olu-llon v@ sFtted tEtE !ro.r 5lonq Eltb the ltbtoo! .uth€nt1c 8&pl,e of [email protected]. aluctos€. mnlose, r.6rrl{toL,
Ealactoee and rhwse. The chldMtoqls r.6 rs !o! 48 hourrtth buteol: .c€tlc acld: rlter (12:3:5).tlE cb!66toqEaa
*a dr!€d .bd spray€d dth aqueu lt 6uv€r nttlate solu-
tlod ln .cetotr€? drled .id ttEn 8trlted *lth aqq@u. 2l6o.lts hyaEo,<ld€ Bolutlod. ethyl dcohol. orly 3 rtDts
corlestDdtlaE to glE@e, 'l6do66 &rtl mnnltol coulil be
ob6€rv€d on dlyltrg the .hadatoaE4,
ao
a0
3o
{!!o
m
ut) !o& ?a! &l 16l'0 ro0 1?@ @ 100 t o
tlnl{0uusrc rcro (irjol t*l[)r.lg. | 2
,l
oat!aaIt6o
6:--€-- 3 so rs rE E s r'o
crr|ouot!€ (rqlol &{)s
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Srllo!llacrrur4|* r€r^rt (c|.crrsol)
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6
liti.RllAcolroclcal, sn Dlrs oLANf, ICTIA'JA (&}&DN',LOSA ASCHERIII
In ord€! to verify the clain tr6t agg!S!3E!E_9134-
dqlo3. contal'ns &tidlabetlc Finciple6 1t eG con6lder6d
aece6satt to stuE the pholnocolosical plopeltle6 oa the actj.v€
$1nclples obtdtDed fln th16 p16ot. The m€thod cnployed {aa
to follo| the b16d suga! lo{€!1ng eflect on .alnj'llstlat1onof thc dlug to !€tlng !a!bttE. th€ retlDd coF]sts of heatlng
the d€plot€lntzed bl@d flltlat€ vlth & 6lkallDe copp€r sul-phate sol,utlon, uhtch Is leduc€d t't, the suE6! p!€Eent yiefdlngcuplous ox1de. a!6eoo rcl,ybd1c or phosphonolybdl. aclal reagont
1s then add€d ehich leects vtth rhe pleclpttoted cuplou6 oxlde
to gl,ve a blu€ solution *hlch 1! cmlE€d ptFtometrlcally {1tha slnil,ally tleated standdd glu@se so1ur1on. abod 6uge
1ore!1nq effect ls th€n lead f.d the cal,lbelltlon curyes.
To tpgln rtth 6tud1€s rele conductrd on tba crud€
{ate! extr€ct of the total plant. Diffelent expeltrents ,ero55
!€lfomcd cccordtng to the h€tled ol t(tng and the results 4edescllh€d ln table !io.12. claph1cal lepreseDtltlo. of the
!€EuItE 1a given 1. !19.16 vhlch 3h{ clearly th6t th€re 6re
no malkeal €ff€ct6 oo th€ blood euga!. ID 6Dothe! exlEEln€nt
blEEe do8ea {e.e adrdht at6!ed, keeplng th€ !.e failDE
tF!1od o! !a hoE6 but here t@ s fdl ln bt@d 8us{ raoib8eryed. Th6 actqal oboervatton6 ale d€6clibed 1n tablc tglDd r1q. !7 . rn the fouorlng e:qE!1ment fstlng F!1od ,sldcr€ls.d to forty tro hou!6 s it ba3 be6n ob€erved !'i' ahr-
otll and ,ltM that by dotnq 50 the rytbglyc.o',c actlon 1t
ey becctres F!€ nEked. t.ble Ia .nd Ftq.18 de6cribe the
lesutt6 of th,ia experlm€nt. In th16 cee al,Eo @ toE!1Dg
of bl@d guE.r r.B ob6orv6d ev4 afte! .ahl,nl,Ete!1Dg tlo do.€!
equtv€I€nt to !oo-9oo mq,ag. body retght-
Att€Dtion ea th€n tqned to studi' the blood 3u9-
4 l4e!1ns effect ol th6 pue cdrpsd cldduloslde. the
ettDd r.s enlalged .Uqbtly .nd iDsteaat of foc !6bbits ured
1n tbe t[evlous experlments eight aDituls {er€ t.]cD fo! thole
expellaenta elch tine. Th€ 3n1GI5 {e!e deplIv€d of food fortr€nty fou! rbuls od onlt $ter ra3 Bllo*d dullnE thi6 tFr-lod. after the r,.1ti.l futj,trg, blood rs collected tt6 the
@Ein.l e$ vle! fo! the gtuc6e deteBra.tloh. ,qu€ds 60l-utlon o! glddulo6lal€ us no{ lnjeted . Itt!!tE!1tont!11!lnto fiv6 r6bblts ud equal volhe o! norhrl ..Ilre r.te! {as
1.Ject€d lDto three rabblr! Hhlch aen€d .. the @ntlol.Blood
6drp1e €e coffect€d !t duferent 1nten6l3 frm a1I tho
eisht !.bb1t5 fo! sugd detendnation tt ktlg'r hlcro ethod.the leeulta of theae e4Ellretrt Be q{v€t lt table6 r5-l8
-94-
.nd the qraph.lcal, .elr!€seatatlon 1B deEcllb€il ln ftgs, t9-20,Althougb i,n lII thea€ elqEriFe.tE Do 6lghL!1cant
bl,ood ausd loreltng e!f*t ya ob6elved but one flct rhlchneeds ne.tion h€le is th.t do 1r nild dose. standulosiit€apFe{8 to b€ hishlt roslcrdr the alt |a15 iued .!ter sdEt1n€. It afso seere evtde.tly cteE that gt&dulo5td€ tDs6-€!3e. 36e bl@d colgulatlog p.otErtle6 elnce blood coutd
not tb taken out of tbe velDe of th€ stha16 sft€! !e, hln-utes of lnletlon of the 6oLurtoD,
InEdte of the lact th6t ln the abov6 e).le!1netrts
ro Fsitive flndiDs r.6 obefled yith !€9.!d to the hylFEIy-c€dc plor'eltles of the pl&t 4g!!9bel;!E33!s!g!9e3r lt ce.ot be 6a1d ylth certalntv th.t thls p]6nt ras no hytDgtyc-
41c act1v1ty. tF.e mrk 16 r€qu1led to trove thls cooclu.t-vely. The prcEent {ork ,a6 only re6t.lcted to normll flstlDganlnals rhere.s studieB must b€ cohducted on etnsl! ,1thorllly 6dmlrlsteled qlucoso and dthals stth allosn lnaluc€d
dlstEt€s befole a flnal csesse@nt could b€ nait.. 2a1it1 !!itxlssa;'hs !e!o!t€d tt6t €xt!.cts ol Eqsenj,a laborua sreeithytbElyc@ic actlvtty *hen .ihl.lsteled ln alloxs tnilqceat
dllb€tlc dlrals but ha6 no eflect ,hen a&dnlatered to no@l
The exporlneDtal detatls of rh€ ph@Bcologlcal
6tudlea ea as follors.
{1) Llesrattop of the plant ea-rracti -40 9@ o! the drleat tbrde!€d pl.!t Ftd1.l r6s
.erluxed rlth 100 nL of <llstUletl rat€r !c lou lbur! In a
6.ut}n€t .![Eatua- The extlact Has @led, fllteled &ilcentrlfused ([email protected]) lor 10 o1.qt$. Af,ter leavj,ng lt over-
ntsht th€ aup€!.at&t 11quid ,aB dec.nt€d .nd €varslat€d toned drtn€88 unde! leduced !EeGu!€. ?h€ !€31ilu€ rls then
6haken rlth 100 mI o! rate! dd f1lteled. ttll,6 tlltr.te v6a
used ln the oqEllents.(1i) E!ep.!.tlon of oluco6e solutloD:-
o.l qn ot pulo arhydro$ glucode vas dl6soLved
1. saturatod b€nzolc acl.r 501utio! (0.31) &at the vol|rc hrd€
up to IOO mI. 5.O hI of thlr stock 6olut1or rere dilut€d ,1thaulDhate
Io0 nr of lEotoni,c sodlq sulpblter@lrlErl:,olut1on ( a nlxtqreot 320 mI 316 N625o4 H2O lnd 30 sl o! ?., CusO4. 5H2o 6ol,utloa8).
ald 6toled 1n tlE @Id.
{1l1) rdn@ nlclo oetbod tor the €stln.t1on o! blood 6uosr-a 6epre of blood (0,05 hr) r!3 plFtt€d out th
a te6t tub. contalning l.g5 ml of the 15ototr1c aodts gulph-
6te-co!pe! Eulphate .olqtlon .nd o.l hI of lod.tirngstate
Eolutlon (loi) add€d. Th6 @ntots eere c€ntrlfused (2000 R,
l.l!) fo! ten nnnutes a.d alloEd to settl€. t hl ol th€ !qtE!-nat&t Ilquld ras ttld plrrett€d out antl pl.ceit ln a tert tub€
cont6lntng I ml of hiaed Hardlng solutlon (pr€tar€d lr€ghly
by ! xrDE equar qudtltl6s o! sqdins ,. 4d H&aling B solutt^F-'
-96-
lhe tert tub. e.! pr@ed ln bolllnE r.t€r to! te! hlnut€6,
c@t€d l. lc. r.ter, 3 el o! glbsplHDlybddrc !c!d le.g€atdld€d ad dllut d to lO hl rdth atl,ltllt€d e.ter. afte lhaltrqr€l,I the col,oa of tbe solutlo e.s ruur€d !'| prpto.€l€ctltc@torti€t€r ullng red ttlt€r (60€). A bl.dr o:qFrln€nt 1r .l!oFlfolmeil dnult&€oualy xlth a st nilud glucor€ 6turLon.rh€ btooal !u9.. 1B c.Ucut.t€d fr6 th€ follorlng equltlon!-
?i:':.i:H' *:-aiffi*i+trk"-'" * iS*IF! IOO nI)
rltEe. Y = r!.nd.!d glu@€ ritlhl.
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c-cc L-QEDFg_ai4xg_-cI5CII$EINAUATI|IA SBAEAOCAIDA A.B!.
The det slblelndldly on th6 dry c4cd€ou! rodk ot tb. t!.trtct o! D.artn th€ loBn6r p!ov1E6 ot atni. tt t..l.o &.ltabt. t! t!.9lclDitlf of 8u&h1 &iit Et'tt.r.b.il. It I. ftrttE !.!p!!.ato b6 gEoh 1D qu.ntlty h thdEtE itt|trte!. tt t. {ro.Uylounil ln tE!emt61 lods iD rblch rE.nnr.L !oor. .r. !trd,Is.t:EteC. It belong! to th. tetly !.rot h'rl.rlG.r. |lrdlr r sdb 91ab!o@ hsb vtth qttrd€rtc.t Fdt rta, olarltrl..ver &a y€rld !loF!s. th. tru.t! l| !ou.a .!al co.trl!,nlnt .e€d.t Ih€ lrqlt torrlltIon tdk . D1... itqri.ng aagsrt-noveb€!. Th€ tn!:dttM h€lght o! th6 9l!nt oo.. lot .&..dta 1rch4 .nd the tr1.nt !. drlt.bi,o.U tb. ?..t !ou!a.
rh. plet ls lotrlully *D-r .. ra.rltEt. o!r!€p.f.tu'bi. It has b6en u!€d by rcd. tos th. t .rt|[tto! aEabctos neuttus. Ih€ it€@tlont o! !!utt, Lov.. togrsthe. rltb IE,:ttoE o! stcr ll.v. b.€! u|.{ 1a tnrrDtC o!a-ltl.oE. P<nabr6d ptst 1. olt€n roqtt€at up to rtoF bJ,.aahg
qrccr, nddetr sd HooF! h.d !€pltcd th. F..-erc€ of alklto1da lD th6 phnt. Thlt r.. .I.o coltllrd !t
59tlsl et .l . Pr€ltrtn ltr clrd.c.l lav..tlgrtlo! o! rh. Dl.|tt
In the raborato!1es o! lEtitule of ct@l8tryr udvsslty
o( Sind had revealcd thc Pr€sc.c€ of sme non-nitlogcDous
principrls a1so. 1t tas th€r€fole constd'r€d desllabl€ to
inv€stiqat€ tlre plant In d.talls dd aLso to cofrpar' th€
prop€rti€s o! thc cmlDuhds isolatrd vith thosL obtained
rlom -ntlcharls 11near1s and inticharis olandulosa tn the
hop. to find out some correlatton of th€ stluctue vith
hadmlytic aclivitY !f 6nY.
Flo. 21 Schuelnfurtlna sPhaeroc"lB' a'ar'@t1ect.a tlon J.choro'
\
trro troc€aur. .d!ga€dt-!o! loutloD5 outJrlaat 1D
tb. aourtdDg tdb[..
fi-E-!-!-:-l:
;€tryr .J.corbr
cooled & !!.tt !cd.r.ddue 4 (PLnt).
{gr--!ll.
..,. ---- B€E€F !ol."i;ili E!Eecd-ne,.€!!ra;e;-r (Eentd.cat!'l€}
eglP&el.€€a
rFet.olhd (50-toqc)
(alrLd)
lettryl lc€trt
!9!!ggrsl,t!I' (c.rDoh'&.t .,rchlolofgm
R€.l-inr.. cblorolori.ol.(unoe! colrEound to. 4Ili,etlqatloa)
The cqrllDhd aAl x!6 ob!.tneit als th. lEl dcohoucextret of tbe ptot oh cooLtng at roff tdtEr.tue. It napqlfied !r:- ^j1::'.: .clutaoi :5!oush a colle of .ludln!eil recry€tallls€d to sj.ve th6 ps€ tro<tkt n.p. l2o-22oc.
It ealy8ed for c,-H-^o- sd lorEed . 2 r 4-dI ntEophenyl bialr-
azone h.p. I56-59oC {ndic.rlng 6 tlee c{bonyl 9!ou9. th€
tnfr&ed sFctls of th6 contDund 8hd€a tt to b€ . .!tur!tddlDhatlc ketone, the Gin band. b€lDg obselveil !t 2900. 1?94,
1460. 13oo, ?30 ed ?]'acnir.
rh. rater ln6olublc !€s1du€ 2 on tle.tE€nt vl,tlr
iEt,eth€r t5o-?ooc) ylel,il6il lnothe! .dlpuod n.p. 164-66oc
ltlch aplEded to be a kcto rlcolDl. Borev€! the cotpudobt.lned v6a very !E11 In qudtltt od e 6@h {s! not twe6tlqltFi.r:the!,
lh. plet reridue obtafn€at !!t6 d19€6tj,ng tleplst vith ethyl alcohol {$ heat€il rlth b€lr€ne 6d th€hFhzeDe Eolurtoi .fter :crc.atr::int lnd c@Ildg ea8 l{lttl€dthrouqh . co:rm of .Iu!l1n. to glve s .t1ihatlc hldlecbo!n.P. 6?-64-c. It e$ ldertlfled as hetrtr1lcontue Ca1%4 !yril*il @Itlns rbltrt yith th€ lutbenttc 6utn€. the u€! c6-tner m.p. 133-34oc sas also 1d€otlt1€il aod d1d not detress
sh€n dred mer+.!n? rtF| n,.a tatren.
The cdrtD$d ss4 ,aa oE.'lned d tr€attn{l tbe
p€t.cther 1mo1ubl6 E€Eldu€ 3 Hlth chtorolorn. It h.d th6
h.p. 95-9?oc dd sleeir ttF pleEene o! csbory1 $ou!t
-l12-
(band at l72oor-r, ln ttle 1nf..r.d feston. rt r., &rsbL.ln be@€a€, ehlolotoh lnd eth€r, .nd iEoluble tn rat*rDd €thyl .Icobol.
lhe si€! solultl€ tb.tton of tt realdu. t r.,dr1€d on ! st€! b.th .D{ digest.d rlth .th!,I !cct.t3.con_caotalted a.d p!.t lt€d bt, p.s.!Dq throuth ! @ll& of .itu_run ro 91ve th€ tNduct fllch tud rct €q,rt.l,tt.. !!o .rry.olvent .ait dlEFd r.n.F!xr 6E!o.Faaun9 to hydlorrt{34ooe-r) .Dd c.rbonyt {l?4o6Fl) grcqrr rt s. ,orubr€10 rat€!, .I@lDl .nd chlorofoe .nd ilrotribl€ ld tD-!ol.rlotveDt!. It folBd 6a .c€tat€ rifch .l.o dtd Dt c.r.t lltse.
tbe 11L oh th€ ch{*terl,E.ttoh .t!t .t.uc!o!.1elucld.tlon ot th€ trlncltils tro the .bot e !,tet scrp€t.-tultht! .ph!6roc!!E t. Ln proG€.. ed rtll be r€Frt€{ellalEr€ |be! coqrr€t€d.
X X! !AI !1 ENTAL
L!9r$&!-9!-g4E9gd_I9i--99r'- "he air dr1€d plot.
sclu€toluthta lprE€reart! (5OO 96), eu cut lnto 8ElIpie.es 6!d heated qnder !€tlq rlth 951 on ! ,!te! both
fo! lht€€ lDqF thlee tlie!. The alcohouc aoLutton tas
fllte!6d ehlle lFt &d all,o{6d to atBbd !t r(M tdp€fat-ur€. ,. cry€talllne prellltate settled itorn th€ n6xt i|!y
ehlch/lltsedr sshed th.roushft rlth cold olcotpl 6rd
!€crystdlt.sd flm ben2€ne-.Icobol (1.1 9G, 0.224). rth6d E.p. l2o-22oc. Foqnd c,?a.69t u,12.66; o,B.65t ca?
H?2o3 leqnlres c'7A.72, A' L2.76, o,4.52. It! lnfrd€dspectrs (!19. 22) 6hoFd bdds at 2900, 1?04, 1460.
l3OO, 7306-r €lpdrg the ltresence of c6tborryl lrouP
oDIy. Tho lroduct raB solublc lh beueDc, chlorofom and
Ft.€th.! (40-6o-c),dd tn.oluble in watelr !ncoho!, &e-
tono ed ethyl acetote.
c!!I99!9r!4!19!-e!-s9l!9.s!g-.ge!, -It r@ ch&acts!16ed .. 5hM In t.ble 20.
-ll4-
!-a-!-!-ri--?9-
Ple*rlttor of 2ta-d]n1t!o .lFpvl hvdiazon€ dc!lv.tlv€.-Ihe csrbsd 361 (50 !l'.) ra8 dlssolv€d 1,n ql.ciat .q€tlc.cld (3 in) lrd 2r4-dlDltrodEDytht'a!.th. {!O m9!) rn
g1.ct6r 6cetlc .cld (3 nl) {r. addeil to 1t.rhe coDt€at.
*!€ he.t€d ob r.t€! fo! t€n nlnuter and ttpt .t rod t6-IElatre rheD the c!yEt.l6 €eDlllt€d atter iorty b1nute..
th€le {e!e tilter€d, rshed rlth 6t6! tholoughly to reDve
acetlc .c1d dd !€crystriua€d a!6 etrtyr &€t6t6? !.p.156-59oc.
l.
2.
3. 2 r 4-di nttEophoyl,
Brdllne 1n c6rb)r
pheoofic o! Enoltchri'dro:.yl gloup 6b6nt.enollc or alcohollchydrr:Sa] gloup ab6ent.
cBbo.yr gloup F€.€nq
Iaol6t1op of coaFsd No. ss2r- lbe llcohouc fll,tr.tc
-115-
ortdned afr€r th€ llolltlon ot conFuril ssL r.. €v.tDr.t€d.rbe r66idue r ss dtgsltod ,lth ,!t6 .!at !1tte!€d. rh€ !.._tlude Z thG obtalred e6s ttelted dth bot.F€t.etbet (5O-?dC,ev6t.l tlhe ed ttE &lv€trt !e@€red. Tb€ troatuct s.tE!3ed throqgh 6 coluM ot d@!m ylth b€nt{€ u the .ot-veat- the chroloptttU b.nd (grs. 1, colos) r@tn€d b.bff!!rd tbe !1!Et tu.crion, (about 2oo !l) on conc€at..ttt g drilc6lj,nt Eav€ 6ft clFtds m.p. 164_6aoc aft4 ton it!y..rh€y r€ra lelysr.Ursed fr@ €thyl Acet6te h.p. t?l-?Boc.lhe cfrrlud uBs ltuufflclent to be tnvesttglteit !u!ths!.I&1au,on of cd6ud No_ !s3i- rh€ Dl$t se.tdu€ 4 dtqlreatinq vth 6l@lFl, r.! ||elt€d uat€r reftu {tth beEeo€trlcc fd thre hors €.ch t1me. rhe lolveot r!! !ecov6!€dsd th€ !€siitue pclft€d t'!l pas.1a, thlqgh c cot6n o!alqlDa rtth benzeDe as the €ruent. o. @rc€!t!!t1i!g 6nd
cootlng . pue ehlr. 6ubltsce hettlng.t 6?-69oc !€IE.t€d.rrE lnflur:d stEctrs .hor€d lt 6it! !t 2950, 2A50, !455r ?30r..d ?l5R rbich t. charlctelj,rttc ot e .l1ph.Uc r.tqr!-
Tr!€ cdrDud i:!! ,olutit€ j.tr berEae,Ft.€th€t !r*tlBol'*i€ in rate!.dcolbl .od lcet ae. It ,ave n€gltlv€El€d€I-cr.lts re.t indlc.tlng fstle lt nor_u@ttc r|.tre.It dld mt d€cololls. b!6IDe 1n elbohtetrebloria€, ,h€hydr@abor fornEd . u.€. lnctusion c€qbo.d D.t. !32-33oC.
-lL-
It lcr Lilartlli€d .| h€atlr,Gotaa. tle tha dra !.D.ol th€ c(lntDsd t|nit lts dcrty|tlve rtth the ruttbnttc lrtit€clrlah€il 116 rrnttch.lls ql!aulo!..ra1atlon ot coiEound uo. 5st4 - Th. !€rldu€ 3 0bt61n.d .ft*the l.ol.rlotr o! coFund saa $. t!.!t€d flth hot chloro!.r-!tblee t1nE . rtr€ chlolotoli s6 !.cov6ed .!d th. !..lltGr€try.trlllreit trqn b€nzorerdcotrol, D.p. 95-9?oc. Itr h!!!_r€d atBtlw (dC.23) slFrd blrit. .t 295O,27tO, lt2o. 1465,1390, tl7o, ?30 6nil 7r5d-1, lt r..r elubr€ L chlorotorlr,tr€D.ene, €the! {ril €thyt ac6.t€,,.t*t lEolulit. In ,.r.!,Ft.etllr caal .Icohol
TiBLt -21 lu.ction.t qloup ard oth€r t€.t.r-
6. !*!i. cblolide
Bro1le 1n c{bon
T€t!d1trdEthlD€
rorn ldchttte-sutF
2!4niD1tro ptFryl
nltroger.hllogan!.nd
ln$taat1on aba€ot?
uE6tur.ti.on .b.6t
PrFnollc o! 6ot1chydrosyl, group !b.eat.60rr.c o. .l@hollcbydro{rr, gloup .b.€!rt.cebohyl gloup !s€!ent.
lh€ csqound ts very !odl, 1tr qustl,ty.o ttcould Dot be r,Neatlglted tsther.Ielrtlon of @h6qnd No. sa5r- Th€ lqueou€ fllrr.t€ ob!.tDedob treatlng !e.1do€ I eltv$te! r.! dlt€d und€! r€duc€d
tfelrse. The adltaouil na. thu6 olralDed ea5 he.t€d ord.!.eflu* rith ethytac€tlte revelll tlhes. Th€ €[email protected]@ 16 concentrlt€d lrd tuttr,€d br rf,llrng thldgha col,uM o! .thin. rtth chlolofoln Bs the lotveDt. rr ruconcent!.t6d .nd c@led, ldt no crFt lttne product r.tobt.lned opto tr cehs. all tbe art6pt! to crystlllts€1t f!6 itl!!e!.nt 6olvent! !dl6d. rts tnflded sp.cJrq(119.24) g.ve 9.ve tE.L5 !t 3400, 2950? 1?4o, 1610, t52o
14?0, 1210, 1O7o 6id to3oft:t ?he product 14 @luble inN6t€r, etlryI 6lcobol, !.etone, sthyl.cetate ud chlolofolrla.d hBoluble 1n p6t.eth€!, b6nzeD€, .nd c6lhoD tetr.chlo-
22 ooD .Dd oth€r t6!t
2. lelrlc chlorlate,
3, Ce!1c nlt!.t6.
4. ?elra-nl'trotn6th.ne
l;.""".*-"*.|
6u1Pha !b!6t.
I phenolic o! enotlc
I hydroryr e.oup ab.at
I e.oltc o! llcohotlc
I lrydrc:.vr erouP Ft€8er
I qnr.turau.on P'eeDt.
I
-114-
lr€D.r.llon of acetvl dcllv6trver- The tEet€ of cqrFundsss (0.s qd rsa d1!.olved ln pyridlne ( 2 mI) .Dd.c€t1clnhydrld. (2 ml) add€d to Lt. rhe enrqt6 rorc h€€led on
! rrter bath fo! tro lDuE ed thd IDEed lnto lce-r.rer.Ttre ra1-3o]1i1 !e3 3eFlrted rhtch uas eaah€d luccesslvelydth dllute aod.blcsbon.te, drl.hydrocilorlc .ctd ual r.tq.It r!! di6lol,ved j.b ethtl .Icohol/treated ,lth .nldt ch{-co.I, concetrtrat€d .nd cooled, but no crysr.l. .rp€.r€il upto
ten d!ya. attspte. *re mde to clystallise 1! f!ot! dltfe.ent6ol,vent! urelthout avllt. rts lnflded sFctlurn {F1q.25)
5h<n€il ab.orDttoD ban& .t 3600 (6 g6tr bard) t?5O, (.tro.q)16.10 (.hould.r) 142a. 1375, l2a't 1065, lO4O, 9OO 6nd ?soq:t
u.!!tu!t,'on lE€aetrt,una.turatlon tf€!4t.
c&lbryl gloup €b8ent.
eate! or a l.ctone
CtllCO ErouD .b€ent.
-rie-
3 '
I a all Iora, ntal (oia[tr.)
Ilg 22
g La
'O
!
o
t!! Sttltlcl!
cnfrru |!$r (|'{.au)rgea
0'.a
-t20-
rooo r@ t0 llo c*r lo lo tp lF
t0
o
0at a t a , , , P rt E u o ,
@s re
cllr'ro nast(a.rrs.t){!g' P4
gaE tutu[ brtQ€r&a)
fr
o
b
l0 l0t | 3 a ? ! t I It C A $ |'
IIg.2s
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-!2t-
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