W. L. Duax

β-Side catalytic hydrogenation and the molecular structure of 17β-Hydroxy-1,4-Androstadien-3-One: p-bromophenol (1:1)

Abstract β-Side hydrogenation of the C(1)-C(2) double bond in 17β-hydroxy-1,4-androstadign-3-one by heterogeneous catalysis is explained in terms of precise Molecular conformation of the steroid obtained fron X-ray crystallographlc determination of the steroid:p-bromophenol (1:1) complex structure. This explanation serves as an example of how conformatlonal details can be correlated with molecular function. The steroid self-association interactions in the solid indicate that great care must be exerted in specifying the total α- or β-side of steroid molecules as the primary determinants of molecular function. The nature of this complex and its implications concerning other complexes of steroid molecules with molecules of biological importance is summarized.

Steroid nitrogen compounds. I. Synthesis, structure, and properties of methyl 3α,7α-diacetoxy-11α-chloro-12α-nitro-5β-cholanoate

Abstract The reaction between methyl 3α,7α-diacetoxy-5β-chol-11-enoate (I) and nitrosyl chloride is shown to give methyl 3α,7α-diacetoxy-11α-chloro-12α-nitro-5β-cholanoate (III) in moderate yield. In the presence of nitrogen dioxide the nitro-chloride III is formed rapidly, probably by a free radical mechanism. On treatment of III with zinc dust in acetic acid, chloro and nitro groups are expelled to regenerate the 11-ene in good yield. In contrast with 5α-chloro-6β-nitro steroids the cis nitro-chloride shows remarkable resistance towards dehydrochlorination, and treatment with refluxing γ-collidine affords only the starting nitro-chloride unchanged. The action of sodium carbonate on III yields 3α-hydroxy-7α-acetoxy-11α-chloro-12α-nitro-5β-cholanoic acid (IV), the chloro nitro moiety being unattacked. The methyl ester V and the acetate VI of IV, and the 3-one VII derived from V are described. The stereochemistry of the nitro-chloride, III, was confirmed by a detailed X-ray crystallographic structure analysis, the results of this analysis being described in detail.