chemistry of natural products (@ummi5je£lir)ir.amu.ac.in/5661/1/t 1321.pdfchemistry of natural...
TRANSCRIPT
CHEMISTRY OF NATURAL PRODUCTS
(@UMMI5JE£lir)
T H E S I S Presented to T&e Aligarh Muslim University
For The Degree of Doctor of Philosophy
In Chemistry
\32t By
HAFIZULLAH KHAN 1973
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m * soviet te fotlom* by & bi,to£ 4f««o»s*oii of fcbo application of tsua »i>eee*OBCopy 60 <I4fc*fp«ie** Spectroscopic oothoU* heve required a predotainaat roto til tit* structural elucidation of natural proiucta durln3 tue la«* d«cade. tbt§ i t epoeiftUr tro» of mm •peetteaoopy vbicU ba* ton«4 tho wttlu»t pocsibio ApI»lft«et;ioa In «trocfcural el^ai^try. tbo totticl otudy
• f tb* *p«etr* Hi tyatic d4t*rp*o**» b*l«ngttt« t* tb* **r* ««*£3«* *fc*l*tal type*. ««• and*rtab*a by tf*afc*rt #£ J 1 * fb**r eaftclualoa*, wbleb *e* #f £tmdaaaatal lapartaoe* to tb£* fi«ld9 *v* dtaau****'* t»* »ot* tapartaat point* Available £?#*> v«c«at Ut*r*tor* at* *t*o to«iud*d ttt kbit dUcttatioa*
lb* •tteoMdios aattar *f tb* tb**u 4* ba**d a* th* «o«k aevrlad out to tb* laboratory and 1* pt*a*»t*d in tw* pa*t*» ***t 1 d**l* wttb t in •t*u*tor* *}f tb* *•* ***t*vtarp*n* aleobol» «b*ilantbatrlol* fHn *(>te«rai ebaractaUatie* of tb* coapouad, i t* d**tvotiv** M ^ transformation product* «t« di*eu*t*d* th* *t*uctur* finally «**&§»•# to eh*tlantbatriol ft* baaad on * detailed anatyai* o* th* &m »p*c&va #f th* «a»pouttd* i t* «*«***•** oxidation and reduction produet** Squatty »ignlficaot 1* tb* caa** apactrai *rasta*otatioa p*tt«yn *jf that* caapotmda irhicb* ba*id*s living up tb* *oiaeolar Cornul** 1* b*lp£ol to asttgattta tb* p**iUon* #f tha aid* abalo and tb* eubetituente* eios*n*tla consideration* aappert tb* atructor* arrtvad at on tb* bail* ol apaetral aoalyala* fhay alao *bow that tb* ca«p*uad «an not ba»* tb* ophi^balan* *k*l«toa, a*sifia*d m • ••» *H*i toau*£l«l*nt *vid*na* to *«oth*» eoostittt*»t • f tbia plant by te»e*«w*»y §& *!• I* traa* «f tbl* partlaalav constituent aould b* toeae i s tb* *»tr*ct •tadlad darina tb* «ouraa «* tbl* vara butt *• *vid*at ir*a tb* *ub*eq»«nt war* on an«th*r plant* tb* constituents
• i pieafca @t©i*f»g in d£f£e«snt ercec ore ©o©J«efc to
Part II d*cl# wict* ifw tftavoaoid eoei*tiCtt«*»td 1
•« iHAtlfti &&IU&1&&* *&* in i t ia l atudi«o «•*• earned ©at wiUb @ sia&M a^oont ef fcl*# leaves o£ cbio plant «®H«$t$d fcom &$%$$ Dun* Mft I oyer chronatosraphy &$ *tk« «stte«t W M M M eh* pfoetneft* 4» vatytna aeounto, of tbroo *luoif«oc*nt *ub»tane*o which ver* iooiofced and Ottawa by «po«troeeoj>i« ttudtoo ouppo»t«d by •ynthooie to bo 6»?*dicjotb©Ej 9S4**ootbyiooediofcy flavanon*, **M* «50fco*pottdiii3 ftavon* cad o related faroaovanooe. Subs«qo«nft f«*««tt§«*ioa of tho trunk boti obtained loootif nhovod tho Bf**#cte« of *i« fluotoocent ©ubotoacoe, tbroo of wbieb cot*Id bo obtaiaod in © c*y»taiUno ototo by tho application of chrotnatosraptiic ootbodo of eopar&tion* 0oo of thoso woo found identical with laneoalatin 8 and tho otfcor wo* shown to b« eh* *dftnothylailyi otbor of ©•hydrowyi&ncooiotin D* Tho chiird conotitaont I t not « truo flcvoooid but boo tho *olo«o<3 diboneoyl ootbaRO »tructttre« tbm iteuctoro oooignod to f t on tho ovidenco ohieQy of 4to aooo i«o***ol fraaoootetion pattorn woo coafirood by aynthotio*
CHEMISTRY OF NATURAL PRODUCTS
T H E S I S Presented to The Aligarh Muslim University
For The Degree of Doctor of Philosophy
In Chemistry
By
HAFJZULLAH KHAN
1973
T1321
Tr32.i
2 < S f P 8 7 < ! -
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fbaftfct ave alto *!»# to ay ««ifca«atte* Cor thoic cooporation and ootJtii diacuooion*
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tlm ««fk dotatibo* i * talft tnotia fa ftatai en taa iavaatigotioa #f too eoaotitaoato of t w ylatttt* * * * * * * * * fiftftfftff***-* f f j f f f f f t (yolypoaiaoea) aftd i t * otkot A tropical traa | t i f f f f ^ gruff***** < Ufwlnttsat) . Taa oonotituoata #f UdUa forao, **«? of *Ma» *?a oood in tho iadtgoaoo* ayata* of aadioifto fc&W ati*octod l««« otteouoa mm §* • * * at ta» * * * * * * plant** 4m* parhopa to taatf iaooeotoAbility* 4 * * * * * * *« f * f« * * * * * coil«ctod personally ftoa fa* Joana * * * * * * §* oortb Sftftla M& t&oir aftt*a«t* aaraonod* 4 «***«aSliM p**4«**t itt * * * * * * * gttitoblo fa* furthoc otudioo, eould be obtained only f to* n ^ f | ^ ^ gfiyip^fi imC wm mmm**&& at f t * * * to bo a 4*®*a4a<l tt*t**jp«n«* S*b**<i*©afc iavootigatioaa •bouad i t to belong to tSm a**j*«*atl**i* rut* g*o»p * f C-2S ««By*«*d*» the aastaf-ta*?**®** *fca aoofc wot I feaov* ooapouiult at §**« gxoap at* * * * * * a» apbioboli*** *M*h bavo a $**»£ aaabovad eyclf* *y*ta* and a a l ia * * * * * tilt a taut at «t«roid». * * * aagfea* *kol«ton of abailoatfcotrial * a t a****** , * i * * t a t t$ that «f <literp<m*a a** i t £ot*a* by a ataeaaft *4*a*i*al to taat raoponoibU fat tft* ataaatatiam * f to* *a*b*a *k*i«taa» * f fc***y«U* ditorpaa** froa gataayl *«**»i*t» a* of g***a*pa*** fires * * * * * * * * * I t oooaetf, taatafora» *»t pazpoaafut to dieau**, in tft* *aa*f*t**ai aootioa* tt»a vary S***fc*6 U&aratara oa ***t*v9**aa vhlon boloag ta *a*f £*£fat*»t * * * * * * taataad taa via******* of ay**** high** «*»»*A**d*t «**** * * * * * froa i ta iapottoaca a* ***** i i aalyfol i a a*a**t**t as
^ 2
andartttndlng a£ tarpcnaid chantttty in ganaral» hat b««n ravitoad. Blogaaati* ttuditt in tnit avaa *t* dlfflattlfc baaattaa of »#*f incorporation «f tba labal I* biobar plant* ami bavn baoa eonliatd far tbia *«**an to ditavpantt aueb at fiibbtffotUc acl<5 and plaoranutittn vbleb at* fungal satftabolitea. Opbiobollne, lite* tbaaa ditarpantt. art alto fungal natabolitat and ttaair blocanatit hat *&•««*#•** feinn tha tubJact #1 v*«y datailad tovottlQattont by $ajt»on*«n aj a£* ffc* <aporc<mc tin-alt* «£ tfcaic atody ©rn *!•# aoacsarioad in tba tbaoraticol taction*
III* invemoation *f tba canttttoante o* i l t , l i l l » smMi&Shm. WG* andnetaMia In continuation o£ tba aariiar worb on ftUlaMt &flg*nalftfcft to tbit laboratory <U2 til alt siB compounds uaro itoiated Iron tbit plant £4va of wbich ate £iGvonoid* and tfaa laet a dibaticoylaatbaoo vbtah nan not bo fasatdnd ae a trua Slovoaoid* l i t lnotatlas along with lancaoiafcin i i t ronarfcabia Its that ponsaaai alto occure along with laocaolatln B lit
Tba bioganatit and cbaaiatry o£ fievonoidt vaa ravlavtd In tvo recant thaoat froo thit laboratory and tinea not ntiob of t ba or a fcicai intaratt bat b«ao ode«d In tba iatarvaning pariod tbit topie bat not baan ravioved ht*a .
ifetAiiifei&iftiwiiiiiAftffiiijfrMiiiRiiBi
3
MfMTttff».. iPtfi fftrlWlWtl, 9fffffI tfrmfffri
The essential features of the acetate raevalonate pathway
to eteroide mid terpenee are now wall netabl&ehed and the
original postulates asaoelated with the name* of Collie* Birch,
nuoicUa, Uobinson end Woodward <i-3) Hove rocoivod concluoive
e&perlmental support Iron the worli with labelled compounds
notably by Dloch, Cotoforth, Popjafc and their co»worHore
f 6,7/K
So & recent conprohoneivo rcvieu by J.D. Oendrickeon and J.fl.Richards 18} tho acetate derived natural products
hovo boon divided into two groups* acetogctiine end terpenoids*
tfhereas neetogenims such as eoumarlne* flavonec and related
phenolic producta arioo through cyclioation of oncyso bound
poly ho to oothyloDO fragmente of vartooo chain lengths* the
ioDodiat© precursor* of terponee are phosphate eetors of
unsaturated alcohols hovine an ieopreneld arrangement of
carbon atooa. 2hte differentiation between tho acetate derivad
phenolico end terpenoid* tafeee place at the level of mevalonic
acid lactone (I) which arise* through fusion of acoto-acetyl
ooeney&e A with acetyl or taalonyi coenzyme a In ouch © way a«
to form a branched rat ho r then a linear chain. The inaodlate
product of thie condensation* hydroxyloothyI glutaryl cooncyme
A (XI) undergoes redeetion of the oetorlfiod earbogyl group
forming mevalonic acid, though the earlier etepe in thie
sequence ere roversable, mevalonic acid once formed lead©
only to terpenoids through a sequence Involving formation of
leopentenyi pyrophosphate (111) its conversion, in part*
to -ft•dimethyl allylpyrophosphate CIV) and condensation of these, as shown, to hydrocarbons of varying chain lengths
differing by 3 carbon unite*
Selvage. 1 o o
sCo^ -f-
CU^t^acetJ " T C o e M 6 ^ A
1 SCoA
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i l l
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VI
^ li^/OPP
v i i
0
The compound* directly concerned with the biogenesis
of di-*nd tritarpenes are geranyl-geranylpyrophosphate (VI)
and fernesyl-pyrophosphate (V). Foroation of squalane (VIX)
Iron faraeeyl pyrophosphate involves the reductive tail to
tail fusion of two farneayl pyrophosphate unite the biocbeaieal
( 9) and stereochemical < *° 1 detail* of which have boon worked
out &y Cornforth, Pop Jack, Lynen and their co-workers ( H,I*9L ).
Cyclisation at equalono folded in different possible ways (s) and subsequent modifications involving a series of Uagner-Mearwei
rearronsaaonts load to the carbon skeletons of all the
tritesrpenee so fa* found to occur in nature*
Because of its formation through reductive fusion at
tvo C13 units the molecule of equalone is structurally
eymoatrical and this structural symmetry* unices totally
distorted by skeletal rearrangement* is evident in the
structures of Host of the derived cyclic triterpenoids.
GoronyI-garany1pyrophosphate being formod by a
continuous hand to tall fusion of c« units does not have the
characteristic »yonetry of squalenc. Apart from this, because
of the presence of the pyrophosphate leaving group the
cyclteation process leading to diterpenee la capable of
certain modifications which ere not possible in tha
cyclisation of squalen©. Thus whereas tha cycliaation of
equalene it essentially a continuous non cteop process
induced by eleetrophilic attachr of tha hydroxy!inn ion-
over looking for tha present tha intervention of squalen*
epoxide- tha analogous cyciieation of geranylgeraaiol stop*
quite frequently at tha bicyclic stage with the elimination
af a proton or acquisition of a hydroxy!. Tha diterpenes
of the labdane group such as aanool (IX)» sclareol <X) are
6
IX
OPP oPP
v\ii
C,OP?
K\X
7
roprnaaatativat at tbia aabaaa* Alternatively tba olefin
(VUI a) dnrivad fto» tba blcycllc lnteraodiate (V1U) aay
interact with tba electron deficient centre created by tha
alia met ion of tha pyrophosphate group! tba ditarpanoa of tb©
plaerane narfoa being than tba lotaedlate products and abietanee
tba products of subsequent methyl alcratloa < \4 ). Wall known
examples of tbia claes of diterpanas ara pinaria and ablatio
aclcs (Kll a, Kill) respectively.
A further point of interact fa tba biogenaais
of tbaaa ditarpanoa ia that though they can hm ©of« directly derived £ro» geranyllinalool recent studios < 15" ) involving Incorporation of if - 8 (•) labda-$»l3»dlone*l5-ol
pyrophosphate In Glbborella fuJi&jiEol to aanoyl osldn ehow
garanytgnraniol to be tha actual precursor*
& very largo aurabor of ditarpanoa ar©»
however, derived from tba cation (Kl) by lnvolvoment of tba
terminal double bond leading to |XtVH which by analogy with
sicillar tons in aonoterpone ehonlstry it represented aa a
bybrid of <KV) and Otvi) or aa tba tricyclooluo ion (XVII).
This ion nay aitbar collapse to give rite to tba tetracyclic
ditarpanoa of tba ataebana (XVlll) Haurane (KIX) and atioan©
(SSI series or survive aa a pentecycllc entity as in
trachylobonc (XXI)<fc)
fbia follow* fvon a angsaatlon by Uookort
( r/ ) that tba carbon aba1atone of all tba tetracyclic
ditarpanoida Own be darivad from tbat of pinaradiana by
protonatioa of tba ayaiia doubla bond* Such a ayaliaatlon baa
boan achieved in situ by formic acid catalysed conversion of
rinuene (wrongly considered to have tba pinaradiana structure
(SIX b) at tba tina) to phyllocladane. Similarly •» appropriate pinaradiana can tarvc aa a precursor of feanrana and
8
*t» tf«ffivatiVDfi* vbteb are aucb «or« abandon* la natur* thui tfeot© of pbyll««ladaa** *h« ater«0eb«ai«ai dttnlU «f th* »¥«•*•• ar» interostlns and «o© b« enalyand ae CoUowtl
Kaor«a« bat a trans<»aaU*<ii« feotffeboftft a* nbovn In (XIX * } • Tb* c«raiaal »i«jreti« ring «yaco0 tan be roeerdod t i t fa t a* a 6*nc»b«rc<l ring #ifeft « two «arbon **!%# or a 7*ttoa!ber«d tta§ with & mm carbon bridge* Th« two carbon btidgo 4« p » tb© <w*a carbon bct^co io oc • ?&•&« L caraoebealnal C«otaroi can origlnac* £row o aation «£ tb« type <£IV * } * ittfttt forwod by dlasiel epproacb ofi the proto» flocl tbc vinyl e*oup Ctoo above on<3 bolou til* platas nf ft lie 8#iA-»tl0ubl© boad af ( i l l «}* fb* roauieins e*«&oti (HIV a) hao A eie Suaad 7-isomt>oro<l riao and a titan* Cuecd ^wooberod cina. ffftgir&l&as o£ the C*t2»U bm& rcirer»o» tM« •ittmtion leading to tb« <tt*r«och«ai«al fectoreo characteristic o£ Imuran* • tStl c) bos 4n feet beon ebovn u b c tit* precursor o£ 9*tydtttykMur«* nolide in galftlllitlffii tl@l*
><l*c\ X M c
7< \ * «
^ 9
It is thus apparent that cyclleotion leading to the
formation of diterpencs te * stepwise process patslog through a
•tabic internedinto IVtlt «) which It represented by diterpenog of
wide natural occurrence. Thte Bay be contrasted with the
cyclisation of equalene which leads directly to tha tetracyclic
intermediate (XXXI). Concerted hydride shifts coupled with scthyl
and bond aicrations transforn this ton in * statically controlled
procaoo to tetra and penta cyclic trltorpeooe of the euphoi,
lupaol and the oC aoyrin a**!**. Essentially a sitailar prace*a
involving 9<iualono Coldod in different nay* la ado to laaostcrol,
bopane and tritorpenco of tba p -anyrin croup C 12> >• Tha re are,
of course, inecanco© of tritorponc* ouch as onocerine <XIUU) where,
because of *i»* fiaootta* fold**® Uh*i**ehU**m$«U****h»te**h*h{> of equalene, (lie cyclleotion pcoceoe ocarting from eithor and of
the Kotocul© ©tope halfway the ouch. \b and -V onocorinc and 1 %
•arretenodiol Ur.IV) are the obvious further modifications of the
cotioa loading to onocerinj the ofaavaatortfttte syenaatry of
oqoaicno bolnc praearved intact in oil aetabers of the Qvoap* The
formation of thesa compounds to* however, a departure frota the
ootomon taodo of sqoalono cyclisGtion.
The above generalisations regarding tha biogenoeia
of triterpenoide arc, however, not entirely correct in view of
the discovery, in i960 by Corey and Van fa«alett f \9,%%) of \
equalene epoxide <34XV)» chemically cvctlabie to an lntareotlng
epoxidetton reaction usins KB8 ( 21 )* as a precursor of steroids
and cyclic terpenoids. Farther, considerations of stereo- \
ehsalstry and the sterlc requirements of too cyclieation process
coupled with the spatial limitations of the aetive eltos on the
concerned ensyne novo tod Cornforth < " 3 > to aagoott thot, at
least, the further Modifications of too Ion CXKU) are not
concerted and involve intervention of an 8 sroup, provided either
10
by the ensyne or the aedium. Tboujh a detailed dieeuaaion of
those featurea would not be relevant to ditorpenoid biogeneeie
it i» eeeential to note that the osycoo at C-3 la trltorpenoa
It atooapheric In origin and the eycii&atioo proeeee i«
initiated by aneyauc protonatlon of the 2»3*epOKido. As against
this in the lorfje nojortfcy ofi diterponoido and eoae tritorpenee
0*8* hynanol { a-4 > and hopanee* proton attack froa tha ettayna surface id directly on the 4 ^ double bond* and oxygen* if it
dooe enter the ooloculo at »©*»© other point it provided by tha
nediura oo OH . the alternate oooefbillty of initial attach by
oifor BgO boo not rocoivod ooriouo conoidoratAon.
A very inportont group of ditorponoo are
charoctoriood by tho proaonco of a p-aubotittttod £uran ring*
Conparioc tho structure of labdane trtth that of polyalthic
acid CESVl^ the loaat complicated nonbor oC this group* it io
obvious that tho fares moiety hao boon derived froa carbons
13 to 16 of tho tertalaal ieopreno unit, Hcrrubiin, eciadin end
androfranholldo^thooah aoro coop!OK etotootttos* ere further
onaapios of eotspoundo derived in tbio tray froa a oioplo labdonic
precureor* la clorodln CKSVX1) formation of tiro furan rinje
froa tho aide chain of tha lobdaoo aUoloton ie attended by
©ethyl nioration, tho reeelting carbon skeleton i« described aa
clarodana (££)« Berdvikiic ocid'«2G) (KXVI11) and tho
ditcrponea of Anonna corlecoa f 27 I and Podooaen «pp« aro <^3 I
farther emanpioe of compounda with a ciorodana obeloton.
Xo their foroation tho intermediate (VIII)
Instead of eliminating a proton directly bao undergone concerted
hydride cod aothyl niQretione tho sequence terminating vith
XXUt XKIV
Esw
H
i^
/
Xxv
- H
CL ! J OK
->Ho
X^vi
^\,oep
• *
KX1X
1
herdvikiie acid*
til an Interacting variation of thia ©cboae
Migration of the C*3 Methylene rather than that of tee raothyi
Ctroup bonded to O A reeulte in conversion of ring A to a
5«&ataborod one* subeequeo* proton eiiaination followed by
eyelieatioo with ill* aide chala teed* to pleuroautilin < XX 111)
toy which the augp.aatad eeheae hao boon eubetontlatcd by tracer
etodiae n^) fee structure son firmly eetabliohod £or
rinuone (HKJi) shous the oporanion of a pinttof raarranconcnt in
0 plaarano derivative. & revereal of tbio proeoee accounta for
the forwation of phyUocladene lEIStl from riouono to m acid catalyaod reaction* So roeenonolactono (FJ1KU) to which one
of too €•* oethyie feet boon osidioad Co & carboayi, £oraatioo
of tho lactone bridG© ts preferred to oiQration of hydrosen
ire© C*S»
Afxart fcoD thoBG backbone rccrcaogoaonto,
rooiniecent of the foraacioc of fvtodolto theouch oEteoeiva
hydride and methyl eittfee to <KKU)„ reateoncononto «ft4 eteavage
rcQofeiono are roeponeible lor oooo of tho aoat iaportcnt
diterpenoids. Thue gibber*!lie acid CBEEltD to derived froa
kcurone by contraction of toe & cine* too carbon atom rcicaeod
froti the rinc ©tructure providing toe earbosylic function*
fojeooie acid (KKEIV) and entaoin <EX£V> provide osanploo of
cleavage of toe C»6,7 bond. An interesting greop of terpenoid a th
grayanotoxinp (XKKVI) ore readily accoiaaodetcd to toe bioconetic
echene at produete derived £rom e pcocuraor auch as fOBVteObjr
eorbanoid attack* aa «bo«o» at C»l* It ia to bo noted that
xxx t t XXX1
XXXU1
-OH
x x x
^ #
XX X W X X X V
^ x x t x X X X V M
u
thaso bond cioovageo hov« occurred in kourano darivativ«»
trfcoro* apart fro* too fact that fofttroogonaoto of t h# type aet
olth to the oisoreoo tovtot ace not posclbia, tho e«otr«l ring
te trndor son* •tyoin bocouaa of the rigidity of the bridced
fc*r«inat pine sy#ten.
fy©» tno Corosoing diecnesion ft to evident
that ait the oajor group* of ditorpcoolda con tie accoooodatod
within fcho fratne-worls of the biogenetic ioopron® rot* I 3 K
fhlo mto t bovovor, in not apparently obootvod by fotorot
imnviti end the diterpenoido imitsalsilcctone and noctlQCtono
f 30 /51 I d e r i v e d ftOB f t *
Wenbert < 32 ) lias saac«efcee" thot farruginoi (KKKVIII) serves ao a precursor of totarot and loado to f t to tm cold catolyacd rearrangement throngfe too etcpa Ottawa* Cetspervoirol (HXHlK) i s cxiothot ditocpeno «ith too uroag location of fit*© Soopeopyl uni t . It to a^cnlflcaQfe fcfeat i t occuro with fotrogfnot end to'caroi in Cupresoua oeooorvtroas ( ^ * •
Considerable interest has be«n ohown to rocont vaara in davolopina avntU«tic echoed boootf 08 Honker**0 hypotboticol tatormodtato iiiVlt) * Sttuo Sut;b Efev and Eopadie < 3^ > found that tHo&ono opossttfo WG» ctonvortcd to tA*teofcottte?i© to a B»- cattUyeod reaction. g©booo.»e«itiy R.D.U.Murray at fil* < 3^) roport©4 a«td o&toiy&od ooavoraioo of ofcoohoao- CXV1U a) toto feaoron© IJIIX a> ieokaur*nc C81B fe* and dtiaitene IKS o)<56J Identical raauiee vore obtained «rito 6ro«!*ylobaa©# From the product rat io and to© *&t«» of totorooovefoiott thoy conclud© that ft bridged ton ©« the typo UVU) oaa not bo involved to ouch traasforoatioao* faoto f o i t i a t oeudi*6 tu.v«* beao
15
considerably attended by lUH.Coftta* *t o l . C 57, 3% $ bttt their c»n*itt«i«** Are aot b«tt«ftll? di f ferent .
A 4it£«?e&fc approach,ba*od on tho emriior work with aqaalcno apoxido, vat adopted by Van Tanoion and Jladflau < 3s ) who found t^ot under noneneyootic laboratory comUfctono tho epoaido CSL) wa» coivoriod to a t?loycU« pro-i.iot <3UhX> with natural eonSigtti'atio**
X V | M a X l x 05 X\x b .
XX a. - X L
><L!
u
Tho etaraochaoistry of tha procoasea involved to tho
conversion of novo!onto acid to iaoponteayi pyrophosphate, ita
isoaerisction to -i'nf *d methyl ally I pyrophoaphate and subsequent
condensation of thee© two unlto to ©ive garaoiol novo boon
studied by Covnforth end Popjok in connection uitb tho
htogeaesie of a qua! on a* the result* bave boon proeontcd by tha
authors in eevcral reviews < !i-^3 1 and dtecuoood also olsouhore
t'Ao U
It boo boon ehovo that the oubstrata in encynic
phosphorylation is only R«mevalonic acid <£&£!}• Mevalonic
acid baa three pair® of diaeteraoBcricaliy rotated bydto-jcne
which interoct differently vith tho chiral aneymo aurSoco.
Studios tHtb dcuteriura labelled aompoundo uero undo ct alien to
porau© tho course of reactions loading to lornosol• tho Important
conclusions of tbio toveotlgotioo ore 00 fioUovei
I. the docarboxylative dehydration of navalonic aaid t^e°
place iron an OJ&&& conformation.
2# tho resulting Isopentenyl pyrophosphate CKttllS) has two
enantiotopicoily rotated hydrogens at C-2 ona of union io
eliminated in ite conversion to -n- dinethyIoilyt pyrophosphate. It voa shown that tbio It the pro»a (Ur> bydcoccn,<pto-6 of
oovalonate)
3. tho protona of tho tloohle hood to iaopontonyl pyrophosphate
*en ho diatioguiohod by isotopic labelling of C»2 of !**•
Mevalonic aoid* If this labelled hydrogen to pro** In
navalonto aoid it will ho trans to tho nethyi group in
iiOpsntonyl pyrophosphate oe In <XblV>. Tbia toollot that
i
HQ.C OPP
Ht?
XL11 X"L ll]
OPP
2-3.3R M.A.2--1 oC-s,'<Ae £«•' fc"-
7-Opp
R-c^Hi-oPP
^ i R
R c
opp ^ - c » ^ Kv
«V\ \ v_i . 1
2) &?P
X L V I KLV
IS
if alkylotion of too double bond takes place from belov, nor*
accurately ffoa too »i f««e« toe n«v chiral eencr* will h«v«
Reconfiguration* By isolating too concerned carbon atom* through depredation to deuterium lobe Hod succinic acid it
waa shown that alkylation toilet piece ftoa below the plane
of the doubt* bond.
4« foe «*thylen* proton* of / ' *dimethylellyl pyrophosphate
<KI*V) con bo distinguished eimilarly by deuteratlon and it con
then bs shown whether elkylation of the doubio bond of
iscpontenyl pyrophosphate involves inversion or retention of
configuration ot this centre. St boo boon established that
displacement of the pyrophoophots leaving group proceeds with
inversion of [email protected]*
Sotto of theeo results ore not in accord with too
ofcorooeloetronic roqoirononte of a concerted process, and
intervention of an X stoop* provided el&hor by the ©odium or
too oo*yo3» as aeafcionod earlier* has boon sugoeeted*
The stereochemistry of gerenyl-geranlol hydrogens*
pro ft or pro It to thue completsiy defined to terns of too
novelono dihydrogens. *"he origin of too hydrogen atoms of tho
derived cyclic terpenoids e*g# kouranc |o thue also knoun.
This knowledge has b.en mode oso of io determining
She storeochoaicol course of reaction* involved in the
transformation of (-)keurano to 7-hydrojtyksurenolide (10.VI)
and thonce to gibberolUno <4i >•
Thus kaurane synthesiscd from 2(a)*, 4tB.)*# Of
3(R)», labelled eevelonate wilt have th* labels* B* ot
positions shown to (XLVtS)*
13
When doubly totalled (2(a)-38, 2*f4C mid 3-(R>-3a,
!***<?] oovalonic aeid wa. added to 9*lftt.ftiUfc faMWHtf aaltataa
lit* isolated 7*hydroxykaur*noUds showed presence of labelled
hydrogens at c-6 and C-7. Thfio follow* froo tha fact that a
decrease df Bt* C ratio was observed on oxidation and base
induced proton enchants* Given tea as tabl tatted stereochemistry of
(KLVl) tbii aeans that h;, droKylotion of riag B required for
conversion to 7*hydrosykaurenolide took plec© with retention of
con£icuration. Another foot which eaergod Iron this study WQO
that tho substituent which i* aatruded from C*6 dotting ting
contraction to gibberellins occupieo tha p position.
Tha •torcocheolcal features act with in tavpanas
and steroids such as tha preponderance of tho trans-anti-trans
riog fusion and to© £*«onfftgutfotion of tho substituent at C-S
are recorded by stork C 4i- I and Eachanmosar ((3 ) to ha tho
direct consequence of tho etsraoolectronic requlroracnts of tho
cyelieotion process. Esporimontal voriCication of thio in
polycyclic ayataats woa not ioaediately forthcomings roactions
of linear ooiyolafina under ae:*dic conditions affording sjoetly
tata froa which only sraall asjooats of tha trano product could
ha isolated. Reliable aitperiaontal eupport was, h©waves,
provided aoma yooro later by Johnson and Kinnel ( 4S 1 through
conversion of (ILf III) to ULVIII3V -
Tha trans-&ati-ctan* ring Junction fta universally
observed oaoag triterpenes hat structures of a number of
dttaraanas vara not in accord with tha requirements of olefin
ayaliaatiaa since availatI* ovidance pointed to a trane-ayn-
baekbone in these compounds. xoa anooaly was finally raooved by
tha iavaatlgatioaa of Scott at al (44 )» who afftad taa svidsnea
26
lo favour of th« eU30eotad trane»oyn»backbon* end found it
inconclusive. They ootod that the stereochemistry at c*f in
thooe caeoo t?&* boeod •sclucivcly on the reaulte of optical
rotatory dioperoion etudico which could not be considered float*
Ginco circular dlettrotitt it bottar suited for this purpoao,
reinvestigation of the etructorag of oafaatot <£&££}»
Bibberollic acid <t> taopioarle acid <Ll) ©tschooone <LIl)»
and ri«u*ne <KKR) with tho holp of circular dlobroiin and x-ray
studios stionod that tho actual etoreochentutry to occh cose watt
th© oppooite of that aosgooted* Tho only reaaiolitg o*«aptioo9 that of apirulc acid eras brought uithin cha confines of this
theory by tho work of Ovorton at al i 4£>»
XLVWa x L V l i i
LJ1
21
fha atapwisa addition of Cs anita, «i
ilia*trotad itt aahama I, toaaa to a halt with * chain Uaftth *f
m mwtbm at«M« *c %*ita*pa»ai ara In raality cot product* of
conaaqutiva Addition but of diatariaation of two c ^ nnita. Tha
ittMtt fte trna of oarotenae, tha C ^ aoapoundi, which ara faraod
by a aimilar fuaion of tiro C2Q unita. Against thia backtround
tha diaaovery of ophloboiina C fc )?tha fir at C-23 conpoundn
derived fvo» garanylfarooaol {fetlt)* was on avaat of aoaa
leportanca itt tha cbomietry of cyclic tarpanoida. Ophioboiin
waa first iaolatad in Japan in |99S from tha pathoganic fongua
ffriiffNJH ftlttftttftfifr raclo*ai*iad lotor a* &tt&ififeftitta
Bivabaanufl. Xta atructura van Qatabticbed almost aiaultanaonaly
by tioto* et ql { u ) in Japan and by Canonioa at at 147 > in Italy. Tha Italian worker• had at firat deaignatod thoir product
ae eoehiiobolin, but in a Joint coanmnicotion *4$) by tha two
group* the trivial naoo ophiobolone fuv) va» proposed for th»
carbon etealoton <1»1V) of the par ant eaftba* of thia group*
Tha bioayathatlc achotaos propoaod by tho Japanese
and Italian gtotipt diffar in aoma raapocta but can atill ba
conaiderad together. Both ara baaad an tha raaulta of
axpariitente in which funcua cultara* wara axpoaad to l80-anrichad ataoaphara* Ophiobollna A,a and C (LV, tVI» LVll)
iaolated ahowod incorporation at tha labal* fa* aitaa of 100 inaorporatloa could ba aatabliahod by taking adventago of
the fact that tha aarbonyl oxyg«na ara aaehangaable ondar
acidic condltiona throueli hyciyc^h^ foraatioa and tha
hydrasyl group aan ha aliainatod through baaa aatalyaad
dehydration. Thaaa atudiaa ravaalod (a) that tha C-ia and tha
9 9 ^ 4
carboayl o*ygen atoao at* etmoaphetic in origin <b) that the
C-3 oxygon it provided by the Medium AS 08* t&gOl and <el tfcat
tan C-iA «sy©e» doe* not participate In the cyciisation. This
loot foUeve ffo» tho finding that (X.VU) vac trcmslornod by
tbe funsus into f&V)t <I-V1> probably serving aa an intoraodiato*
to tho echoa* aofggoatod by tbo Japanese oorkorecq-))
eolvolytic diaplaeeeont of tbo pyrophosphate group establish©*
tho C-l,ii and C*»|0*S4 bond* loading to an intermediate cation,
past atructuro UVUI) which in stabilised by doUydrotioo ct-Viiia)
Subsequent reduction and oloctrophilic insertion of OH*
providoe the bytlroayi at C*iA which tforna the ether tialtago
with C«l7«
fan fcoro olobotr to uorU oC Canonice et *J ehoued
that this sequence ia uniifcoly, einco C«14 waa found to contain
trttiua o£ covaloaateU- H) orloin t so} which ie inconeiotont
with (LViild) as an intovnediatsj.
In an eorlier study tboee authors < 51 I &?a«
tfco fungus in « gteditift containing 2-3U navalottats. If
@etrntiyi«£affteaol Ulii) or it* biochemical equivalent is
asettaad to bo the precursor tritius label* ahould appear at
position* ahovn in (LXK)« Presence of activity on «arbona-4»an<i
24 or 25 woe readily «»t&bli«tt*d by dehydration to CS>X) anil
cl00voce to givo acetone with Oy To check the sites o£ nativity
in the root of too nolecule (LVD vae o*idisod with HBO^ and
the diearboKyiic aeide foraod vara separated aa their notbyI
eaters. Comparison of the activities of thoea aaida ehoved
that 016 eartiod Z tanaltad hydrogens, in agreement with bioaenetic theory* but surprisingly % labelled hydrogen alaa
showed up at C*l3. Besides, comparison of too activities of
(LVD, lUC! and the dicer bony lie acid esters sucgeetod that
c> 9
*11 Che | 0 i*to«il«d h?droaa;»» o5 awv&loaato oslgin var« pr*««nt ia CliVSI vhoraaa 1 should feav* ooaa loot gm fc&a **»•*»&«* o2 fctk* 7#3-double bond. A Uydiride too $*astaf«itf 2sro» C-t> fed C-lS woo invoHad to acoouttt lew «&• auonaloaa labell ing and th* proposed bios*actio »oboo« As 6«vffg*d to docoaaodac* tthoa*
1st « lr,ta* otudy i t van 8hw» ftfe** tSts hydrorjan trantf^rrad from C*fc turn ftto <c attftSiswrafttaft And that
pyropho9pJ»oJ« to HA fa tto^atanat;« &$ setabllshotS £»* squal^ne*
HO'
YIP
. / '
/
^
v w (
r< OPP
-^ c \
\ .V\ t i
•* S
ivin o-
24
Ths ehaaistry *f cystic ditorpaaolds wag raviavad la if W #y MetitIndia and ovarto* 4 S*i 1 • fit* iatarvaalng period hac saaa eonoidarabl* addition to «lt*> Hot of naturally occurring diterpeaas providad by than* pharbal I S3 > ©nd portalai I b^ I reprassating tha *ora intarasting nov atruaturaa.
1ft th* sastertarpaaa fiald th* aeyslie precursor of ophiobolins, geranyifarnasol* and i t* ally!4* isomer gsrenylaaralidoi, have boon isolated, th© foraor froa insect mm t SZ} ftfi* latter fro* th* tongas **tlittlgiltlftllii < 5 & l* The eyelio coapounds caroplastota CUC1) < 5 ?) based oa tha opbiabalan* skeleton wera aloo identified a* tha constituents of iaeect *msv Tha aariaa cpongas of the flffffajft group <5-,b^> have yielded the itttaat soateirtorpeooe ircinin l and a (Lail,LKlU) and *a*di*ulatin UKIV). the aoat recent addition i s . that of retigas&oie acid <t.EV) which i s a constitoont of tho Lebaria group of liehaat < cc I*
A survey of tha literature #1 the last few yaare revaals that classical methods *f struatara determination involving dehydregenatioa to known aromaties aad degradation to atmpler fragments* though s t i l l applied, have boaa progressivaly replaced by aadora spaatroseopia techniques, specially NMR and mass spectrometry* Se-dehydrogenatioa i s avan now resort ad to ia establishing fundamentally sav carbarn skaIatoas bat th* aapariaantai proeadara has baaa simplified by tha ass •£ TLC and CI»Ct spaaially th* lat ter . All saparatlng aad identifying th* fragment* forasd ia this drastia reaatioa. Again* oiassieal sequence* for degradation *I th* *|d* chaia and oxidative a*thods Car ciaavaga of tha earboayalio riag syst*m, ars at i l l
6 0
CM iOY\
L * l &
CVUOM
uv\ b
v*tt
Lx\u
L X J V
oH
uxv
fr«qtt«fttly tmevoidabU < &J- t bat application #f RMt «paat*oie»py at e l l »*&&•* i&§ »ad« tba tattt of itttarpratiag thm tatult* «•«& aasiar* tt«t# •p«otr<M»try> baaidea providing iwaediota atmfirwafcioa of ill* aolocular walght, •f tan a probiaa vaara prasaaca of a attabar of oxygon atoaa aakaa | t diffiault to daeida batvaen alterncta foraulaa* *att fornioa in favourabln «aaoa» ail tha tftforawtion naodad tor atructurai datarainatloa«
In viaw of i t s pro*araitio»t position in coooteal and oteraoenc«ieel invo*ti0ationa tbo wore Import ant aapccta of tlw application of HHft opoctrotcopy to diterpence or« briefly dioaussod hero*
28
Hiffltig j f jgl t i t t iftftHfiOT gPtHSKfllfiffPf*
The soot characteri«tic Coaturs of tho SHE opootf* of otofotdo and tetpenes ft* tho oethyleno eavslop stretcblttft If on »•© - 6 .ft (*> end the ah&rp signals of too aethyl ©roup* projecting abov* i t* fho position of tfco methyl oSgaoi* to dopcndcnt on tho Interectiono vtth eubstitusnts or uncGturatlonc in other port* of tho molecule* to which tho sotfeyl protone of« ©r.poocd* Tho odditlvlty of theee interacttoB» woo dononetretod in otoroide fey Enrchor I GM end ho© sine* boon ©Ktonelvoly ostoloited io structural worts on attologoog cyelio fyttoms* In trttorpenoe, with © larger nurabor of noneqeivatont wothylenec and up to O-acthylo en oaturctcd ccrbooe* GOcigotaoate in this ronton are nuch nore difficult ooi i»mt& not hevo boon poenifcto but £or too batter reeelutlon cvoliable ©ft tOO tic one: the uoo of colvaat induced ehiftf f f i .tq). Dltorpoao apoctra arc comparatively loo* confusing la thle res Ion and oro Curtisar oiapliCiod by tho. foot that ons of the C«4 fiothyio i f frequently ct & hlchar onidction lovol, or to altogether aloetng oo in t0*nor coopounds* The soot proninont contribution© in thio otoo wore SKHSO by VJonUert and hio coeociatofl who carried out eeaoorenant© on & largo mmber of coapoundg to c.rrlv* at reliable general i oat tons f 6«r»*<>). fhoir sarlter exanploe wro dravn froa tha tricyclic diterpenes of the ableteno group hut o conparotlve otudy of too spectra of tho ptnarone group «aa Bade in a subsequent coanunieation (67>«
wmmmmmimm—Bmmmimmmmm »• m r a i n w — > »
<*> Choaloel ohftfto oro re ortad ia r valuo* throughout tho thesis*
o r* A, if
fit* position and auit ipl ie i t ie* of tit* proton* MI carbon* bonded to oxygon and tarbonyl functions, and on doubl* bond*, aire fc«lpful in loeatins *fc* position of those function** in cyclic *y*t*** coupling pattern* can *ft*» tin vary conplicatod but with tho vory eon«id*r*bl* aaouot of dot* nov available * full end accurat* analysi* of coupling con»tant* i* *eido» oeoensary*
A ohorootoriotio foatur* of tbo obi*tie acid group of diterpono* l« that *fft§ C i* h»ra frequently aroauttic. Ill abiotic acid, and tho ptamric acid gf«*o represented by pinarie, sandoracopiaaric and ioopinaric acid** tho eorboxyl at 6*4 i* oqootoriai vheroa* In podocarpio acid i t i« OKial. Xhoso differences m%* theoo coapouad* a suitable choice for coaparativ© study«
fh» KISS opoctro of dehydroabietic acid <l*SVi) podocorpic acid (Utvil) « ayn^hotie analogue (tKVUI) and their 7-koto derivative* ©hov tho offoot of otruetural Sana*** on tho position of tho signal of tho C-10 aethyl and *tr*«* tho iaportonc* of conformational effect* in oyolio *y*teia*.
M
\_y \>v\i
In thn abeeoce of aubetltuente an 0 4 an In UXV1U) ting » nnpntlnnnnn oaly the distortion « | bond sag*** fcYoagltfi nhant hf ite tttnin* with the aroma tie ring an* in in the half ebelr fa?** f&* epatiel requirements af substltnsttts o* C«4 fore* It to eeeaae * half-boat aoafiornattoe. thin conformational change in enfantta* in the relative positions, 8.7d end • • • 3 , of the C-IO methyl i» UKVl) an* <IXVU1> respectively. The greater deshleidittg experienced by the 6*10 mechyl In i&SVtl i« duo to tho fan* that An tan holt boat eooforwatlon o£ ring S It i l brought nearer the dashielding soae of tho aromatic ring, wttnm deebieldtog by tho aronaelc ring i t oot n fnntnt?n# in ooodoroeopinatic acid} tho C-tO methyl signal I* further op-field at #«S9#
introduction of a too to function in t»4 relationship to a fta&hyl l« aoroally aoaoelated vith alight doehleldlng of the oetbyl. the paramagnetic shift of tho C-10 methyl signal to e.74 and $#% in 7-keto derivative* «£ <i4«rct and <X.XV111) respectively i« in accord with this but the eatent o£ d©shieldins, 0.04 and g>#|| pp» $$ low vhen compared with 7«fceto steroid* and pimaronee »h«r» \~ • 0.20 pp». thin in attributed in port to flattening of thn vim* eyeten mring to •pahybridieation of thro© ndjnnont carbon afcon» and in part to the 4*«w*m* in the aoisotropy of the carbonyi group through ite conjugation with the aromatic ring* Thn a t i l l lover value* o.oe ppm, for f*hnt« <UtVl) in again due nn eterle feetore, thn C-lO methyl belag pnt very nan* thn boandry «ff thn deshlsldlns eone of thn earboayl and thn shieldleg earbenyl eone*
The axial and equatorial methyl alga ale merge intn nnn (at ninglat) In thn am epeetrnm nf dehydrnabietadiene.
ft *t
bat •*# «•****? diatiaat in *** Wttt** of ***** ditarpanaa and aro ttf£«et«d to di«£ar«at axtaato by othar aubatituanta in
tha Moloauia. Co»pa*iaoa with eoapouada ft a which «4«§ C it
byd*oa*o*atie «*g* piaarana *** i»opft»ar*o« darftvotftvaa vavaalt
tba datbiaiding of tha «•* »*thylt »* •*• *ro«acic ring ill ^*
d«ei^etv«* of dahydroabiati* aariaa f#»s* dahydroabiatadiana T4*«#* f ***** »*****»* *»4 4Wi»a««Ji» 4ofi*a*4*«# *&»* #•!«!»
That if* axial aad aquatonei «-* oathyia «Kparienca difforant
intavaationa with tha 7-kato function i» ahovn by compartaon
of 7.katodahydroabiatic acid with 7«-«atOpod«ca*pie mM* Tha
crootar daahiaidtng of tba C** o*ial aathyi of 7-keto <LSVl)
find* ita cauntarpart io tha d«9hl«idio$ of the aarboaathoxy
aethyi of ?.tu^oUXVU> which ia abiftod froa tha ooYt&ai
poaition $•$$ to 6.25•
Other important oboarvationo in thia aoriea a?#t
a> fbar axial C0jB» coa» and CHO group* at ©*4 &&#« & shiaidlns
$££««* oft tli« C-10 »atbyl . II tlia C-* twtbyl ia «o»t affactod by tba oaturo of tha
aubatituont mi C*4 and ia daabiaidad by o.23# ®*M* ##M* 0*4* pp» by ftaighbourina C30» 6^fi« COjR and CH Cuactioaa. thia «*s affaet ia tha aafla in podoearpic and dahydroablatic
aariaa* Coaparftaoa of «&* poaitioaa of the aathyl
ticoata io tba ao»daracopi«a*ie# pimwi* «a* iaopi*arie acid aariaa ohova analogotta latoroctiona batvaon aubatituanta and •atbyl groupt. Of particular iRtaraat har* ara tha affaata of change of ataraoehaoietry at C*ti and tha poaitioo of tha double bond.
Thfta earlier atudy of tha *arloue *arurally oeturrinft trieyalie aystena •>«• extended to bicyella eyeteae (leaden* deriratlree) by F*&«Jef£criee f fe© >•
o 9
The sptetnl tte**ureftont« of * variety of if#1*4 i3fit«a»»«p*«tikliy steroid»# here eetabliehod fh#* th« -
equatorial protest* in thm &t>e«nce of othor feetore, ere deefclelded eowpared to ills esiei one*. The reeeone tut thli
have been diecueeed |» * etftjtderd test C <se I on the tfubject•
III teirpenotde the *ethylone pretone #1 euhefcitutod angular
and aesiaol Methyle ace aleo ueu&liy »on etjtiivatcot and
eouplioj between thew c*voe riee to veil defined A & quartet*
with targe coupling oooetaote. Thie ts due both to the
restriction of free rotation and the neyianetry of the
adjoining corbon*
The hydro*yeethyl group on C-4 con be either
asial or equatorial. Provided that ©•$ ie not eubctitutod the
tuo cypeo mm he diatioculeoGdi the quartet of the aeiel hydroxywethyl croup hein© centered ot 6.3 and that mi the equatorial at 6.65 < vc ) . Both quartet© ore ehlftod
porcaesnetically to 5.C and 6*23 reepectively 00
ecetylatf on € "7r * '/a > •
Farther eupport tor those Atcignittcnts can he
obtained by oxidation to the oldahydo. When the aldehyde
function li equatorial the cidehydic »*©t©» appears ot 0.77
tthoreae when tt is aslal ft appears at 0.23 < 73 )•
the deehielding of the angular OlO ©ethyl
hy esial earboxyi and carhomethony troupe on 0 4 hacs 01 reedy
heen referred to. Thie effeet lo *lao evident fro© s etudy
of the Kttt epeetra of several kaurane deriv^tivco having
different eubotituente 011 C-4 reported by P.R.Jefieriee |<7{ I.
J t>
St hao fco«t «t*4 i» Mfctt§ eoaUsurationat a«»isnMnt» «ft C-A but to do thin tha chaaieai ahift of tha C»|0 wathyl in tfc* p&raat eospotmd «ru»t be known* wham thla i t not tb* «aa« rcauction of COR to Cfl involYiQfi ••tef&i «tap» i* neoattary*
la tttcb ««••* a sort aonvenfant and diroat o •
proeadara iateoduead by c»a.Ha*©yonui (74 ) can ba tsittf* fli|« ia bo»«d on tf»* Coot chat tiaco praacnca of a actrboxyl or a aavboMathoxy function in l,3*dlaxioi relationship to o ©othyi 1 aorta Jto thiol dins of tha ©ethyl croup the anion of tit® oeid autot daahiald in tho aanw relationship, thn corraotnaM of tbi* ageunptlon vas ootoblt«ho<l by tumour ins the apactro o* iO oclda and thair eecaro I® pyridine.
fjjMuKCaaflBiapililJiil^
The interpretation o<! tho clc«Gle o£ tho nothylcnc proton© adjacent to a earbonyl function i# di££icult ot;Ans to the Xona-rGnco o££ccta of tha eorb-oayl croup ( 7j> ) and tho conpioa epin interaction* of thcea protons with proton* OB naighbourins oarbona• fit* bcee induced a^chen^e o£ thaeo protons with deutariun la froqaancly halpful in •ttafeliftttisig tho position *f the oarbonyl g*«»p in tho aolacalo o»fj# t3acarcn^onol <76 J#
JwwwiiMiMMEiU
ChoiIantnoa farlnoaa Snolf• (silver fern) grovs
os the alopos of mountains* in the Himalayan region in north
India and Hilgrl hilU in the south* The material used let
tat present otttdy WQB collected «ro» the Jaamti region in
North India and a specimen of It was identified' by the
botany sectioo of the regional research laboratory, Jammu.
A ourvey of the literature revealed that the
flovonoid constituent* of ChoiIanthoe fagittoaa collected
froca Taiwan had been studied by B.Srdtmao who identified
two kaenpferol derivatives (;?7>. Similarly the Initial
•tody of ftangasfraay ©t ol uao also restricted to the
£lcvonoid conatituenta t"7§J*
Itffil nf ItR, , st SMl% tafctelflil * Catrection in sovoral botchoo of the corial
parte of the Cern with licht petrolcos In a soaulct affotdod
a groon solid mase which van col lee tod and reCluicad ©ovorol
tieea vith licht petroleum and finally for a briof period
with other* The ether insoluble Material was purified by
repeated crystallisations from ethyl acetate to give cryetale
of cheilontbatrlol a#p. 102?
ChcilonthGtriol is eoluhle in most organio
eolvento oat its beacons solution form* o Jell on cooling*
It give* o faint pink colour with acetic anhydride/cone. H2S04* * t o , t •Poclfle f o r tritorponoe and steroida hot the
colour remain* here anon lighter than la ueuel for these two
typee of compound*• The Hoilot reaction with tin and thionyl
chloride is aiao positive but again the intensity of colours
developed is not th* some as with ttitotpenai* On TLC
plates cheilathatriol and its derivatives give a dark blue
colour with an alcoholic eolution of pbotpboaalybtlic acid which UGB, therofor©, u*ed throu0hout the voifc as a epray reagent.
Elesentary anal y s i* of chcilanthntriol gave the foilowing value*i
G# 76.52J H# i i . 3 3 | Act. hydrogen, 0*71%
These values, anting allowancos l o t purity of the aaraple and
esporiinantoi error* agree with c24H4o°3* C24fl4a°3 a n d
C2 5
H44°3 * o r which the required voiuee, on the assumption
Of S*oots*vo hydrogana in the aolecule, are given belovs
C26H4003* C | 7 6 * 5 5 1 H» *$•** #04 active hydrogen, 0.73Z C24UAa°38 C* 7 * , l A s R» tt«!8 and active hydrogen, 0.78* c
25 ia4403> c» 76.48| 8, i t . 3 3 and active hydrogen, &«77$
The Baas epectrum of cbei lenthatriol , however, ehowe M at mfo m 37A which ie not in agreeaont with any of the formula* given above end require* the molecular foraula C2Aa38°3# A P ° , a l b i * ftKplanation of thie anomaly l i e s in the eoeuoption that M to in foot the M* - 8*0 peak which would
leave only one for aula in the running • Cg-B^Ov* M ehould
thou bo at m/o 392 and M* - » a0 at the observed value 374*
correepooding to C£*,B42®$* T h l * c o u l < 1 n o t » »*«***** be coneiderod certain f i l l further evidence in eupport of th i s aeeuoption wag obtained and the taolecular formula G^^Q^
which require* C, 7#***» fi* 10.291 active hydrogen, 0.80 hed
«•)
to bo included o» a poaeible alternative*
In pttnclpU the iccua could have bo«n •otttod by toting «s oe«ar*to »&•• •pootru* of tht t r l o l whuh would fcoiro diotit*fiui»htd ootwoott C f4 t t l» e * a n d
C25B4a°2 b t t t t b t * * P * e t r u " c o u l 4 n o t ** •»*&*«**•
fiffjflfffti tffltftl
OV. *no 6V «pectru» of choilantaotriol f fttg*S> show* on oopatoat ooKtoun at 220 ota but too oBapo of too oruv* to aovo lifeo that of too cu*ve rosottsa* f*o* ond absorption of ftoototod double bonde. Tho »a«i«u* #oft thon oo oooottfitod for oo o oooooqttoooo of tho Itiotronoot cutting off at 220 ma. fhta point «1U 6o roturood to I at or vhoo th® apoctruo of tho oxidation product of the alcohol to oo»fE<2»i?od#
J 4
U . Tbe l» tpeetrun (Fig.2) •how* OB etvetebing between
1SO0 and 3300, C • C *tr«tcbinS at 1635 and CU$ bene! log ©f
tbe gov dimethyl grouping «t 1363 end 1390 *a • ffe«
chareeterUtie ikolotttl vibration* of the ge* <i loo thy I group
tl2IS»lt99iv,(7^0 c a" n o t »• «•**«*«* with certainty mid
ere of only theoretical Interact, the tit «po«tru« thut cetab«
lichee the exietenco of uneaturation and hydroxy! functions
i» cheilanthatrlol and give* «ouo Indication that it« corbon
skeleton Is aiailar to thot of Ct aaC triterponee.
2000 l«00 l 6 0 ° FRECIUEI1« I CM"1 '
SIM* *&• Sua spectruo 160 Me) of cbeiianthatriol (Fig.3)
shovs the characteristic datura* of the spectra of bigbar
eyelle tsrpenoide with aost of the protons coning to resonance
ia tbo high field region of tha spectrum betwuan 0*00 and • «£•
38
Of tfc* two mltftplot* dow* ti*14 tit* a** eonttod at A.3I **» bo **#|ga*ti t* *» #l«£$8*e ©f*t**# whit* th* otM* «*nt*od *t #*00 §*» ** a«etgo*d t* protons of tho £g*OB ft******** Xi til* **•«* ** ttuft latograt <§ diw«> **•* tfe* Kultipiot lit 4*5a io takoa, a* A v*£*t**«* til* auitiplot At *«0 tat«grot«« ft* thrao proton*• Th* t*t*t ttuabor *f proton* fca th* atoUeolo o* tt»i» fe*§i* work* oat to~*cu
if
5 o PPM (6)
— < i i ^ ^ — — w i- „ B B W B g i f
Doth th* r t t l* of til* r|M of tfe* ttttagrd ***r til* aethyl signals ** «*lt ** th*tf roUtiv© heights ami width* thow til* prcsoneo of f&v* tertiary Mthyls, tvo at *«|* I* 6fl) «** *** *A«h *t 8«$S» «#•«» 0t9ft* fti* broad signal At Q.it soggssts further th* prsssneo of oft* olofiioic aothyl* If th* spsotrus Is Mftiuttd oft*# ohaUing th* «ti^lol*t* solution
39
•f tkt la ipU vit* DjO tho signal t* tlMi o&«flnic »»thyi kieoMi tfettptt «•* tfct g t tvt t t t i t th« fetigfct *l tat §»«tgt*t #*t* i t *•«•**# i t rtpU««n«nt t f thr«t prott>at vitfc 4««t«rtti*. Ttiit i t i t ft* ttfctn* tMwtvtt* *t <mty m tportsiattioft* ft* signal t i t to olsclnie proton sppsars Co b* • tssntUUy * f f i t t t t wfcteh i t further spl i t fry long-ting* inttrasttons* Since thsrn art 3 proton* of the £8*011 typ* uhoss signals o*«rUp i t i t not ootsifeit i t analyst *t» oultiplet at 6*0*
Attsaptac ecatyiation o£ tfftoUanthfttrftiM otta t se t s t acotic aobydriCo &o4 a <e« drop* »« nyeidiitt <Hd not soececd GC f&€ tf the oily product obtolnoO o£tor work op abotJod i t to be a alsturo. 4 crystalline «6*tate woo, fcowovar, ttediiy ofetoincd wb«n oqooi qoaatUieo of pyrftdiot and ocotic onhydrto© wars osetl.
200 250 300
WAVELENGTH (MILLIMICRONS)
350 390
p i g 4
40
mm QV •p««t«uitt H tkm t««tst« (fie«<^l §h9&9 &neAm nhm H&4 lolling «ft«iitttis m a£l tt» alone «ttti t.tm i»ll«««i«tt
J
4000 3000 2000 1500 CM-I 1000 900 800
7 8 9 IQ
WAVELENGTH (MICRONS)
12 13 14 15
Hit IR •{>««ttiui (Fid*»l ft* «9t« t«£oeii&6t«tt •ti09tiis v *Qa «t HSO 0*4 Mf^flttyl al»»»tptioii i..t t f99 fm& l?4<l • a *^ * A i « i i « i t i M«Mt« t t f i s i *«««iit« kftftdt «t la io «IKI i2io»
fOTMltiMI of « 4t«t«tat« Vllt«tl i « Al«« i n l»OC0ttf Vi%%
«»»ly«i««l t«t t t lM« But M t « ftgAiA t!l« 4ii£<iff«ae« in tb«
,t«i|<ilv«4 ir*lo«» tm € i8 ^stimott ^^i^J^i^ ^^ ^tt^At^i
fovMilAii f« t %%m «t«««t«t«* il«riv«d Ml tlM %m%m of
SA^'di^d oftd ^l i '^M^i ' ^ * * ^ ovtsi»ol «o«p9«n4# to not
imam%0m* flM mltt^tiiat i«s ^AAII «ii thm fraAi* «f •ittiiMr i«v«t l* is •s«iii t t t 9v«i«fti itt t i l * «Mi« iiHMittiis «iittli tkHttA «|f«t«jit li^'«t ni t 414* tlila tttt««* «Hli ii^*fO on tll« » • • ! • «f «s«B4ft9ft • 4 f i *M 8^ • 4a OS tlui %«ol« • !
•w<^ ' T H P l i^
€ ^ t ^ o ^ « 4 i i * f l i t ! • • • « i fto t«tt«»i>«»i« to «tk^ «ii A««ii« «eid And i»£ 48 itt fcfa«i «f l^t#iB4 hi^ #t i^i«ii
flMl itift •i>«et«ttit • ! tiNi 4ll«^t«it# tfi@«4l •luiPi tti0 «M$«to^ Mittqrlt nt ?«t9» tlnr«« f#»t«iM)t^ts at s»it# #«!$« #»id I t 3 •«t«bi ao^ t i ^ lit i«(}t l« 4ai»
i-O PPM(T) 6 0
S 0 PPM<8I 4 0
Is»t««4 • ! tli« t i9 VAti* b#tv««a t M two fioim fi«t^ wilt i9l«t« i » t i l * •peotvitii * f i l » •le*li*t» tlM •psetvoft of tl}* ae*6*t* mUmm * t « t i * «f l t | * ttit» • • « • •
z
t« »#ir ftfp«vi«pt«ti «» t in t of ilHi tftvliiiitt ftftton* iHl lkt
i*MM^«tQ4 t i« f i^t«ft«tii I et I «iMl tuft* ! • tiM i i t t t
«)!» {)r«»#ii«« «f tilted lijrStfi^id in felM »»l#ei>l* tit wtii«li
ic« «99ll0a «a4 e®taiitfk @<! ait«« S fliltt«e««* C]ltMMitdgr«iplti«
« i fill* aiiii}«tQKft d£ior4€d* aitov «93r«lidili«#et«ii ftiMi
- I
th% um iip««tvuii lfi&8«7l |>rdvt4»i €itritt«ir
at 9»f i* fiM «itii«i »s %im ^«£ii it« Mitiiirt <»% «*ao iia*
|»tfc «R i.Mt«««ft«ii •§ Ittvt6«t sytftifctiis 6xm to toat left i -
«r« ii«6r«y %li« valtiii* tli«|r ^im to iit» «ti«tii«l «Q«i »tui4
4 o
«0n{»l«tft i«p{t««iMI «fi « I «!MI ai i f idt* ^t l^tnt i t « l d irAitt«»
SMHi
50 PPM{S) 4 0
i i l t t l« «l l«iO « f I t t i t * Sllfi»ll« «(SiO l>4l A«0ftdik*<!l V i t lk •MMI
««Yfia&ttty t » ^tt£ififte> A«*til«3r •««tiyt(Mi« lGgj|*dft6l ait4
•&{»«• t« po««ftt»le CO ^«t#ratfia thus^ e««it»ii&@ eoiitcafict of %w» «£ tti« nii lt i |>l«t** fl»» •i$ii»t of tit* ttl«ftat« protOB £« a CftAfljr v«tt <l#iifto4 t v l p | * t irtftli l<ifis^v®at« iiltftira«fti«li»# l« i« «oiif»te4 IJF • 7 «P»I «o tti« CJl AAtt l v»«oMi t i l * 4otibl«t of «lit«li i » «&»« Cuirt&ttv •p i te t>f AltfJkfte #i>ii^liA«« ftift» tftftv^i mlf %hm btoad AM pw^tm
4 4
Df tti&» 9f«t«3i Sam not !»• «Q«ttsr tti{ir Aik«ly«e4[ i t fti ^p^mmut ivtm tb« «id«ii at ihm cistfat tlwk I t in nmpim4 to ii9V« elittii ««» py^tdiMi* f b i * #9«eitvii« ««iif l«t*lf iii)w« ixp fthd ni tiisrt 0 i tiM «»yft«ii £im«Ki«itt tn «lMiAI*ttBllAt»iol cui »hmm felmii to t»«l«»0 §• pw$M»!tf0 •#«4Hi<Sayy «ad t«vttovjf Iiy4f««yli«
If) t%ii ttsid ti^etinitt « i tti« aMBi«acotat« tiift s»«i at iiglwfft wm» mlnm i« « t H^^ tliat i t #jtft«tly « i tlHi ^mm v«A<t* #• iA t%m Qi^«iitt^i 9i tlw 4tiifi«tftt«* thH iiQitl^ #etf««fi«n^ «« ll '«Mi tlMi hm%» of ilM> •«le«iilar i#iMilA ^g^^^^A ^^j|4^|f% «06^flgl i«y tli« mmme»^&t9
nm tr^oyo-ao in tiMi i|>«etfBti ol th« dl&eittet^ tte« ^cli at 9#e 4 t i ii» tttosiit I 15 SI Ilk t&i^ ofi tlio «9i»«&«»«ot# I t i9 l>iit0lf ¥lei61« m4 mm attvilittt64 «wmi«^«lf in tbs ««rljr «t£{ses «£ titoir«rii to ttASft® ot tim 4A«««tdt«
ft«»^laci«ii v«A«tAoit ¥m a&t«iA#d t»y tv*&tn«ftt 4»t %lm dtm««tAt» «£tb Al««iltoSls Sik<M« or ui^ti ttiMQ^ t« otiief» v%i9h sdtii l>«elit ti»i «tay%i»s natoetcil* aclo t&'Vd Iqrdttly*^* ftf til* ptgwAvp ntdtafilt faaetioa eoold «iS«0 Im . K « . t . d »t»fc » . ,00, I . <»|.<a««b.t .« t M a WporoWM bat oo f aythoff ut« vat aa<{« QM tti» ^9»Mooe4tt# ti)9t)|&&ii@ gyoit t l i l t
offeotiK} &ot& trmt WtQ^&M^ itntf t<l/e ClOSI tm a»tlt«ti<it*
4 ^
f&e « i tli» iydtiiiitteltioft |^t«iiMft ili«fMitf I t i * i « * «i i^«f«
^UJM f««tt«tl«» «IMI t»» «•#• Cfl^wK i « iditMi •i^tk*! iSKiWitt* i;lit««ftt«iv«fti3r m^9 t l l i « i i gul l *d %# tlMi A»«lA»t«ii # t %%m
t«l^««ied «ty««ft|li«iti««( l t d * ^it&iii# • i««v ti&l«li i t n t l t t d
fItC iliiNwtf t i t » IMI «rait«»iiii«i«4 bf twi^im 9^ ^ « firo<ltt«i
^•iMM»%«| «fia||r«i« mA iM»tiiwi Ii3rdf«8«it ii««&iii«iieii guve tlw iNil^iitl lit fatwita ^^^^^^^ #li|«& I t
«ee«ai^aiii0d %f %f4w^W9lf9i** f ^ tE apcti^ytts CPii«i l mppm%» t i l l * iui««rpv«ciiiti^ «tti>i/»a8 st ssin <»tf iMNiciyr fpl§A%m t%M» 1itoa4 ibaaA !»?«•§»% &» tli» «f««t«eii tti tli«
«»ttiit9ii««i #fi ttift t « t i i # t y tlydtttaorl steQ* I t i t «! •« 9VM«iit a« ^m% tim #« • • vain* &« ttm tfftttftYita •< « I M
4%B*9ptmM0umm of tlift jBbt«Yfti<m at« to t l « 4 Q I ^ I O %««« «t l iS f «ft*^*
fliOMi t«»til«« tuggootftd tl ioi «»• of «ii«
4 6
mam • • '<^
35 4 0 70 6 0 t o o I IP ftO
4000 3500 3000 2500 2000 1800 1600 WOO [200 IOM" 8 0 0 ~ FREQUENCY (CM' I )
P l ^ &
Cfttbeii o«oft end eiiae «ti&ii te ttm sfteo&aary liydcoisyt t#lt«ti7»
l ltatAtar* alioirfti ftli&t tl it* tfp* of imlfeiptfit i t «ltftt««l«ric«i« o< AHatttt^ I I ^^-ol* < ^2 l# «tt9»« i t t«tolt« ittm «q»at toaplti^t of tk« C»tl «itt«l |^v«t«ii wttk «ii« •tttal f tftioa* «» e*t awS G*it «iki«li gtira ttaa ta a tliiraa iftaa faftfeata* ftMaa tliraa atra ap&it aftata hy iaftavaattaa vitik ttea C*ia a^aatavial fvafcaa aa aa ta tive t&aa ita a ilaoblat mi trtplata* Aaalyaia af ttw aaltli^tat at 6*0i liaraa
4 S
5 0 PPM C6» 4 0
lii»tii iiitt md^At pfQtcsitt ii«« io«& i l l t i i« fl«tli^l«M» «iiiNit«p<6a>>
i a t l i*ft lMit! i t tt»tol *
tm •it««i»«»t vfLttk in* &hmm itti«ir|ir«tatte«
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