Reaction of phenylhydrazine with α-substituted epoxides and ketones. Intermediates in osazone formation in steroids

Alfred Hassner, P. Catsoulacos

Research output: Contribution to journalArticlepeer-review

6 Scopus citations
Original languageEnglish
Pages (from-to)121-122
Number of pages2
JournalChemical Communications (London)
Issue number3
DOIs
StatePublished - 1967
Externally publishedYes

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211-213", which is also obtainable from 16a- bromo-17-oxoandrostan-3~-o1 acetate (VIII) with phenylhydrazine in 70% yield and convertible into an osazone6 with hot phenylhydrazine in acetic acid or pyridine. Compound (VII) probably results by phenylhydrazine addition to a phenylazo-inter- mediate similar to (I). Bromo-epoxide (VIa), m.p. 129-131", also yields (VII). Epoxides (VI) and (VIa) can be obtained by peroxidation of the corresponding olefins. The reaction of bromo-ketone (VIII) with hydrazine takes an entirely different course from the reaction with phenylhydrazine leading to the 16-hydroxy-17-ketohydrazone (IX), m.p. 209- 211". Here the reaction probably proceeds via a hydrazino-epoxide analogous to (VI) . This work was supported by a U.S. Public Health Service grant from the National Cancer Institute. (Received, December 19th, 1966; Corn. 101 1.) 1 Previous paper: F. W. Fowler, A. Hassner, and L. A. Levy, J . Artzer. Chem. SOC., in the press. 3 R. N. McDonald and T. E. Tabor, Chem. Comm., 1966, 655; C. L. Stevens and Chung-Chang, J . Org. Chem., 1962, J. Buckingham and R. D. Guthrie, Chem. Comm., 1966, 781. 27, 4392; A. Hassner and P. Catsoulacos, ibid., 1966, 31, 3149; 1967, 32, in the press. Identical with the phenylhydrazone of cholest-l-en-3-one. L. Caglioti, G. Rosini, and F. Rossi, J . Amer. Chem. SOC., 1966, 88, 3865. A. Hassner and P. Catsoulacos, Tetrahedron Letters, in the press.

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