Steroids XLIV. Synthesis and D-homoisomerization of 3β-acetoxy-6α-(N-acetylanilino)-17α-hydroxypregn-5-en-20-one
Summary1.The reactions of 16β-bromo-3β,17α-dihydroxypregn-5-en-20-dione (III) and its 3,17-diacetate (IV) with aniline have been studied. The reaction of (III) with aniline leads to the formation of the 20-anil of 16α,17α-epoxypregnenolone (V) and the reaction of (IV) with aniline to the formation of 3-acetoxy-16α-(N-acetylanilino)-17α-hydroxypregn-5-en-20-one (IX).2.The hydrolysis of the diacetate (IX) with potassium carbonate in aqueous methanol has been studied. The hydrolysis is accompanied by D-homoisomerization with the formation of 16α-anilino-3β,17α-dihydroxy-17β-methyl-D-homoandrost-5-en-17a-one.3.The structures and configurations of the compounds obtained (V, VI, VII, IX, X, and XI) have been shown by a series of chemical transformations and by physicochemical methods.
Mass spectrometry of steroid systems.—XX The application of the ionization efficiency curves to some stereochemical problems†
The dependence of the cleavage of some cis/trans-isomers in the terpenoid and steroid series on the energy of the ionizing electrons have been studied.
Mass spectrometry of steroid systems. IX. Stereochemistry of 14-hydroxysteroids.
Abstract The fragmentation behaviour of 14-hydroxy derivatives (I, II and III) of rac-dehydro-estrone and rac-dehydro-D-homoestrone under electron impact has been studied. Configuration of the compounds mentioned has been based on their mass spectra, the mass spectra of the corresponding dihydrogenated derivatives (VI–IX, XXVI and XXVII) and the products of thermal dehydration of the latter (obtained directly in the inlet balloon of mass spectrometer) as well as the mass spectra of the deuteroanalogs of VI–IX.