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019 TEE STRUCTURE

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

On the rtruotureof Moeoorine

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

pentanone than with a osolohexanone

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.

10 D.E. Ayer,G. Gohi, P. Reynolds-War&off and D.M.White,J. Amer,


them. SOO, a~, 6146 (1958). 11

L. J. Bellamy, The I.R. Spectra of Complex Moleaules,Methuen,


London (1958).

l2 Samples were generouslyprovided by ProfessorA. Stoll and Dr. N. Clauson-Kaas.

On the structure (2) That Hofmanu degradation oocurred very readily of

of Dioscorine the oxotropane (now known to be at 30). although

IV) methiodide Thiele it

(aqueous

sodium bicarbonate communication, which, of 10

not referred

to in &hive since

more recent
6-oxotropane,

becomes

even more curious eliminate

the two com-

pounds,

should

more readily, the weight for of

ie unaffected the evidence there

by the same reagent. 13 definitely eupporte piece

Thue, although Pinder@a structure against (II) it.

Dioscorine,

remains

an anomeloue

of evidence

13 The degraaation [M.R. Bell

product,

P-oxotropane,

haa been eyntheaiaed $2, 6147 (1958a.

and S. Archer,

J. Amer. Chem. Soo,