OF DIOSCORIEE
T.L.V.Ulbrioht ' University Chemical Laboratory, Lensfield Road, Cambridge (Reoeived 29 January 1939) Diosoorine by Pinder2-7 had shownthat the alkaloid AFl!ER Investigations has eitheratruotum evidence in favour I or II, &ohi et a1.8 presented
CL
NC
co-o
I
-
HC CH,
CH-CH*
I I we ct%
=q-i;crT;a
NMr CH,
Me
o-co \
Me CH~-cH
I
I - CH, I
CHdH-CH*
I
II
of I. It wa& subsequently shownby Pinder9 that this cannot be oorrect, ardthatthe ooneot structure must be II. 1 I.C.I.Fellow. 2 A.R. Pinder, EatureLand,$6,!, 1090 (1931). 3 A.R. Pinder,J. Chem.300, 2236 (1932). 4 A.R. Plnder,J. Chew Soa, 1823 (1953). 5 6 7 0 A.R. Pinder, J. Chew QOO, 1577 (1936). A.R. Pinder,Chem,& Ind, 1240 (1937). A.R. Pinder,Tetrshedron L, 301 (1937). Congress G. Gohi, D.E. Ayer and D.E. White,XVIthInternational
Paris,July 1957. of Pure and AppliedChemistry, 1000 (1938). ' J.B. Jonessnd A.R. Pinder, Chew k hi,
5
8 !l'hlr struotureIs now supported by &hl.lo His earlierevidenoe la favourof struoture I was as fallows~ (1) That the ketonederived by degradation of the laotone ring -1, band In the infra-red at 1730'0111 (i.e.,III or IV) had a oarbonyl
1723 WI? (CS2) lo and that this was In better agreement with a omlostructure.Pinderhas already pointsd
out 9 that this Is not so; In faot, aooepted ranges 11 are 1720-1706 om" for oyolohexanones and 1749-1745 OIII-' for oyolopentanones. It is relevant
oq-
CH -
CHI
II I
III
NM
CH.
i T-i0 I
ihk
a CH,
CH,
cw,-
CH IQ
CH,
the oarbonjrl frsquen& in to oonsider more olossly relatedoompoundsr , and in 6-hydroxytropitropinone (j-oxotropane) ib at 1722 om-l (Nujol) none l2 at 1705 ox-' (Nujol),1715 cm" (CC14).This clearly supports the
oyclohexanone struoture (Iv) for the ketone, aud is oonfirmedby the position of the carbonylbaud in 6-oxotropane(III),' whioh IS at 1750 -1 cm # as expected for a oyclopentanone.
(aqueous
not referred
to in &hive since
more recent
6-oxotropane,
becomes
pounds,
should
Dioscorine,
remains
an anomeloue
of evidence
product,
P-oxotropane,
and S. Archer,