Free-radical oxidative transformations of androst-4-ene-3β,9α,17β-triol 3,17-diacetate(Article)
- Department of Chemistry, Faculty of Science, University of Belgrade, Studentski trg 16, P.O. Box 550, YU-11001 Belgrade, and Institute of Chemistry, Technology and Metallurgy, BelgradeYugoslavia
Abstract
The oxidation of androst-4-ene-3β,9α,17β-triol 3,17-diacetate (2) with lead tetraacetate resulted mainly In β-fragmentation of the C(9)-C(10) bond to give a mixture of 10α- and 10β-acetoxy-Δ4-unsaturated 9,10-seco-steroidal ketones (3a and 3b) as the minor components (in ~7% yield) and the rearranged 4β-acetoxy-Δ5(10) -unsaturated 9,10-seco-9-ketone (4) as the major product (in 61% yield). Unexpectedly, when the same substrate (2) was subjected to the mercuric oxide - iodine oxidation, it underwent predominantly α-epoxidation of the olefinic double bond to produce the 4α,5α-epoxy derivative (5) (in 58% yield). © 1988.
Funding details
| Funding sponsor | Funding number | Acronym |
|---|---|---|
| Serbian Academy of Sciences and Arts | SASA |
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1
Further eluates contained 4oc:,5-epoxy-5o(,..androstane-3/3,1713-diol diacetate (7a) (72 mg, 6.9%), m.p. 1760 C (from methanol; 54 mg, 5.2%) (lit.IO m.p. 1740 C). IR (KBr): ~ max = 1738, 1730, 1247, 1235, 1047 cm-I; IH NMR: S = 0.81 (~, H3C-18), 1.12 (~, H3C-19), 2.05 and 2.10 (two ~, AcO-3 and AcO-17), 2.90 (~, HC-4), 4.60 (!., HC-17), 4.95 (~, HC-3). The next fractions gave first a mixture of 401,50'-and 4/J,5"-epoxides (7a and 7b) (58 mg, 5.6%) in a ratio of ~2:3 (estimated from signals in the IH NMR spectrum obtained for this mixture), and then 4/J,5-epoxy-5.G-andro5tane-3~,17~-diol diacetate (7b) (51 mg, 4.9%), m.p. 920 C (from I I acetone; 42 mg, 4.0%), (iit. II m.p. 93-950 C). IR (KBr): y max = 1738, 1730, 1240, 1040, 1020 cm-; H NMR: a = 0.81 (~, H3C-18), 1.05 (~, H3C-19), 2.05 and 2.12 (AcO-3 and AcO-17), 3.18 (~, HC-4), 4.60 (!, HC-l7), 5.15 (~, HC-3). Further fractions afforded testosterone acetate (8) (160 mg, 18.1%), m.p. 1380 C (from acetone--methanol; I 121 mg, 13.7%) (1it.12 m.p. 1370 C). IR (KBr): 1 max = 1730, 1670, 1245, 1040, 1020 cm-I; H NMR: 0 = 0.83 (~, H3C-18), 1.20 (~, H3C-19), 2.05 (~, AcO-17), 4.62 <,g, HC-17), 5.73 (~, HC-4). Acknowledgements - The authors are grateful to the Serbian Academy of Sciences and Arts and to the Serbian Republic Research Fund for financial support. They also thank Dr. G. Lukacs (C.N.R.S., Gif-sur--Yvette, France) for a generous supply of starting material.
- ISSN: 00404020
- CODEN: TETRA
- Source Type: Journal
- Original language: English
- DOI: 10.1016/S0040-4020(01)89810-0
- Document Type: Article
Mihailović, M.Lj.;
© Copyright 2014 Elsevier B.V., All rights reserved.
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