hlay 20, 1959
STEREOISOMERS OF
2x79
IO-~IET€IYL-~-DECA\LOL
(presumed to be the dichloride) rapidly evolved a gas chloride evolved hydrogen chloride to produce 11.Ya in the dry state and changed in crystalline character Confirmation of this lactone structure has been obto form a product which, although it oxidized iodide tained through study of the reactions, described ion, had a lower iodometric equivalent weight than below, of I1 in dilute solutions of potassium iodide the theoretical value for iodobenzoic acid dichloride. and sodium hydroxide. Complete details are Because of the instability of the dichloride, plans I I to study its equilibration with its components were Ho-l-o, coob C = O abandoned.
i)H- I1
c1-1-0
- ,+ w I-
&
y
O
H
\
given in the Experimental section.
O;;&'
Acknowledgment.-The authors are indebted t o ~ 1 behavior , ~ which has been described was the National Science Foundation for a grant in supnoted many years ago and explained without con- port Of this research* firming evidence, on the assumption that the di- DAVIS,CALIF. [CONTRIUUTIOS FROM THE CHEMIC.4L
LABORATORIES O F NORTHIVESTERN
L-NIVERSITT]
The Stereoisomers of lO-Methyl-2-de~alol~~~ BY ROBERTH. BAKER,L. S . MINCKLER AND ALLENS.HUSSEY RECEIVED h-OVEMBER
8, 1958
h n improved synthesis of cis-l0-meth~-l-2-trans-decalol( I ) and the synthesis of the trans-trans isomer (11) of the cis-cis isomer (111) and of the traizs-cis isomer ( 1 x 7 ) by procedures which permit assignment of configuration are reported. -Absorption bands in the infrared spectra of these and related compounds appear t o be diagnostic of the nature of the ring fusion geometry.
Two of the four isomers of 10-methyl-2-decal01 reduction with lithium aluminum hydride. In have been described p r e v i ~ u s l y . ~ -Both ~ of these spite of the nine steps involved, the over-all yield isomers melt in the region of 65-70' a t very nearly of I is 3 5 4 0 % and the product is much less subject the same temperature. The p-nitrobenzoate of to contamination by isomeric impurities. one has been reported to melt a t G5-G7°,5,7 the IVhen compound I, prepared in this way, was 3,5dinitrobenzoates to melt a t 110.G-111.2" and a t converted to its p-toluenesulfonate and the latter 07.5-98.5°.4 The isomer which forms the higher was refluxed with potassium acetate in acetic acid melting 3,5-dinitrobenzoate has been synthesized -acetic anhydride solvent, the epimeric acetate was from a 10-carboxy-2-decal01which forms a l a ~ t o n e . ~ formed in 25-30y0 yield. Considerable (ca. 30y0) Also, when oxidized with chromic anhydride, this elimination accompanied the displacement reaction. isomer has furnished 10-rnethyl-2-trans-de~alone.~ Saponification and a chromatographic procedure on It is therefore cis-10-methyl-2-trans-decalol( I j . alumina led to the isolation of trans-10-methyl-2We have found the p-nitrobenzoate derivative trans-decalol (11) m.p. 59.5-90.5". The p-nitroto melt a t 71-73'; hence it would appear to be benzoate and the 3,5-dinitrobenzoate of I1 melted identical with that described by Yanagita and co- a t 153-154" and 122-123", respectively. Thereworker~.~,~ fore the second isomer previously reported4 is While compound I can be prepared in three not the trans-trans isomer 11. steps from 2-methylcyclohexanone by way of 10The synthesis of cis-10-methyl-2-cis-decalol (111) methyl-A1~9-octal-2-one,3~4~7~8 we have come to pre- and of trans-l0-methyl-2-cis-decalol (IVj involved fer the synthetic sequence to 10-methyl-2-trans- the common starting material, 10-hydroxymethyl-2 decalone, as developed by D r e i d i ~ ~followed g,~ by cis-decalone (V)lo as follows: V was converted to its p-toluenesulfonate V I and the latter was (1) Presented, in p a r t , before t h e Division of Organic Chemistry, 129th Meeting of t h e American Chemical Society, Dallas, Texas, reduced with sodium borohydride to a mixture of April 8-13, 1 9 X . the epimeric 10- [p-toluenesulfonoxyniethyl]-2-cis(2) A grant from the Iiezearch Corporation assisted t h e carrying decalol isomers. By way of a fractional crystalo u t of this research. (3) E;. C. d u Feu, F J. hIcQuillen and R . Robinson, J . Cheriz. Sac., lization procedure, the epimeric p-nitrobenzoates 53 (1'337). were separated to furnish 177, of the cis-cis (4) A. S. Husscy, H. P. Liao and R . H. Baker, THISJ O U R N A L , 76, isomer V I 1 and 71% of the trans-cis isomer V I I I . 4727 (1953). See footnote 3 ior t h e naming convention used t o desigThe former melted a t 114-116" and showed no nate t h e geometry of these isomers. depression of melting point when mixed with an ( 5 ) R?. Yanagita and A. T a h a r a , J . Org. Chein., 18: 792 (1953). (6) A. S. Dreiding and .4. J . Tomasewski, THIS JOWKFAI,,77, 168 authentic sample cf V I I , 1n.p. 115-116', from czs(1'355). 10-hydroxymethyl-2-cis-decalol. lo Similarly V I I I , ( 7 ) .\I. Yanngita, I;. Kiamakawa and .4.T a h a r a , J . O r e . Chem., 20, m.p. 161-162", did not depress the melting point 17fi7 (195.5). ( 8 ) See F. D . Gunstune and I
