ステロイドの研究 第30報

Cholesterol及びCholesteryl Acetateに対するN,N-Dichlorobenzenesulfonamideの反応

抄録

The reaction of cholesteryl acetate with N, N-dichlorobenzenesulfonamide (Dichloramine-B) under the conditions used by Fieser in his oxidative reaction with N-bromosuccinimide (NBS) produced two hypochlorous acid adducts, (A) C₂₉H₄₉O₃Cl, m.p. 195-196° (yield, 48%), and (B) C₂₉H₄₉O₃Cl, m.p. 186-187° (yield, 7%). The melting point of (A) coincides with that of 5α-chlorocholestane -3β, 6β-diol 3-acetate. When (A) is heated with alcoholic NaOH, it undergoes saponiicatron and at the same time an oxide ring is formed to give the known cholesterol β-oxide, m.p. 131-132.5°. The acetylation of (A) results in the formation of 5α-cholestane-3β, 6β-diol 3, 6-diacetate. (B) is in complete agreement with 6β-chlorocholestane -3β, 5α-diol 3-acetate.
The reaction of cholesterol with Dichloramine-B under the same conditions as in the case of cholesteryl acetate produced only one hypochlorous acid adduct, C₂₇H₄₇O₂Cl, m.p. 165-166° (decomp.), in 23% yield, which corresponded with the compound representable by 5α-chlorocholestane-3β, 6β-diol. In this case the isomer having C₅-OH and C₆-Cl could not be isolated, probably due to the formation of this compound in a small quantity and the coexistence of several other compounds. In accordance with the inference by Urushibara, Mori, Fürst, and the others, these compounds are believed to have the above-mentioned structural arrangements.