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New Synthesis of the Cyclopentane Ring 1687 eluate (B), Table I, in vacuo to a dry sirup and acetylation of this sirup resulted in the isolation of a colorless sirup rotating +93.4°(c, 2 in chloroform). This acetate, dissolved in ethanol, crystallized overnight at 25°. The total yield of pure octaacetyl-6 -[ a -d -glucopyranosyl ] -/3 -D-glucose, [a]25d +98.0°(c, 2 in chloroform), m. p. 143°, was 9.2 g. or 77%. e Crystallization of 6-[a-D-Glucopyranosyl]-D-glucose.-Six grams of (IV), [«¡25°d +98.0°in chloroform, was deactylated catalytically with barium methylate at 0°. The barium was precipitated with 0.5 TV sulfuric acid and removed by filtration as barium sulfate. A colorless solution, pH 7.0, resulted. Concentrated in vacuo to a sirup and taken up in ethanol the deacetylated material crystallized during several days as long prisms. Recrystallized under similar conditions the sugar was separated by filtration, washed and dried to constant weight at 98°. The dry crystalline substance melted at 120 °and had an equilibrium [<*]2Sd value (c, 1.2 in water) of +120°mutarotating downwards. Its Jlfcu value (c, 1) was 97%; yield, 2.3 g.

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The scent of the common skunk (Mephitis mephitis) is so extraordinarily powerful and persistent that from time to time it has attracted attention from chemists. That some sulfur compound was present was recognized early,1 but it remained for Aldrich2 to show that the principal odoriferous material is «-butyl mercaptan, accompanied by alkyl sulfides. Almost simultaneously Beckmann3 noted the occurrence of

¿\s(i4)"cholestene (300 mg.) was oxidized with chromic acid by the same procedure as used in the oxidation of 8cholestene,8 and the reaction product was divided into a ketone and a hydrocarbon fraction. The ketone fraction was indicated to contain a mixture of ketones since a crystalline product was not obtained either directly or as a semicarbazone or an oxime. The hydrocarbon fraction on repeated recrystallization from acetone-methanol yielded 12 mg. of A8,I4-cholestadiene, m. p. 83-84°, which gave no depression in mixed melting point with a sample of 8'14cholestadiene obtained by the action of perbenzoic acid on As(n).cholestene. A8,14-Cholestadiene was recovered unchanged after being refluxed with maleic anhydride in benzene for nine hours. Catalytic hydrogenation of A8'14-cholestadiene in ethyl acetate with palladium catalyst yielded a compound in the form of needles, m. p. 52-54°, which gave no depression in mixed melting point with A8^14kcholestene.Bromine Titrations.-The cholestadienes were titrated with bromine in the same manner as that described for the titration of 8-, A8'14^-and A14-cholestenes.s It was found that 3 • 5-cholestadiene, A6,8(l4'-cholestadiene, A7,a^uj-Ch0lestadiene, A7,14-cholestadiene and A8,14-cholestadiene in chloroform solution consumed 1.01, 2.24, 3.04, 2.66 and 3.22 molar equivalents of bromine, respectively, dissolved in chloroform. Using a methanol solution of the compound and a methanol solution of bromine, the same compounds consumed 1.02, -, 1.65, 1.76 and 1.83 molar equivalents of bromine, respectively.The authors wish to express their appreciation to Mr. . M. Gladrow of the physical chemistry department for helpful assistance in obtaining the absorption spectrum data. Summary 6•8(14)-, (11)-, 7•14-and 8• "-cholestadienes were prepared. The methods of preparation and the specific rotations of these cholestadienes were compared with those of the known analogous unsaturated steroid derivatives.