326. Steroids containing ringAaromatic. Part I. The dienol–benzene rearrangement in C₁₉series

Abstract

By E. CASPI, P. K. GROVER, (MRs.) N. GROVER, (MISS) E. J. LYNDE, and TH. NUSSBAUMER.Several deoxy-steroids of the C,, series with ring A aromatic have been prepared by the dienol-benzene rearrangement, and the rearrangement is shown to take a uniform course to yield the 4-methyl-substituted compound. Dehydration of 4,17a-dimethylcestra-l,3,5( lO)-trien-17@-01 yields the exocyclic-unsaturated 4methyl-17methyleneoestra-1,3,5( lo), 17(20)tetraene without structural rearrangement. This contrasts with observations reported for other series of steroids. Transesterification resulting from the decomposition of lithium aluminum hydride with ethyl acetate has been observed.

Condensed Cyclobutane Aromatic Compounds. XXVIII. α-Bromo Derivatives of Benzocyclobutenone

“…(3) For the first report of the synthesis of a benzocyclopropene derivative, see R. Anet and F. A. L. Anet, ibid., 86, 525 (1964), (4) Analyses were performed by A. Bernhardt, Mulheim. Melting points are uncorrected. Anal.…”

Biological Activity of Certain 4-Methyl Ring A Aromatic Steroids.

“…Five 4-methyl ring A aromatic steroids recently described by Caspi et al ( 1) were studied for steroid hormonal activities (Fig. 1).…”