- A 19-nor-4-androstene -3,17-dione method for the preparation of
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The present invention discloses a 19-nor-4-androstene-3,17-dione preparation method without chromium oxidation, wherein 19-hydroxymethyl-4-androstene-3,17-dione is adopted as a raw material, is subjected to 2-iodoxybenzoic acid oxidation and sodium chlorite oxidation in a solvent, and then is subjected to decarboxylation under an acid condition so as to obtain the product 19-nor-4-androstene-3,17-dione. The preparation method of the present invention has characteristics of no requirement of use of the hypertoxic chromium oxidant, high yield, high raw material conversion rate, easy oxidant recycling, and environmental protection, and is widely used for the industrial scale production.
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Paragraph 0038
(2017/04/03)
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- Steroid dimer formation: Metal reduction of methyl androst-4-ene-3,17-dion-19-oate
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Two isomeric dimeric steroids, 3,3'-bis(methyl 3-hydroxyandrost-4-en-17-on-19-oate-3-yl), with symmetrical (α,α') and unsymmetrical structures (α,β'), have been obtained by reduction of methyl androst-4-ene-3,17-dion-19-oate with zinc in aqueous acetic acid together with the major products, the isomeric methyl 5α- and 5β-androst-3-en-17-on-19-oates. The structures of the dimers and unsaturated products are supported by spectroscopic methods. The symmetrical dimer was also obtained from treatment of the 4-en-3-on-19-oate ester with lithium in ammonia. Copyright (C) 2000 Elsevier Science Inc.
- Templeton, John F.,Majgier-Baranowska, Helena,Marat, Kirk
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p. 219 - 223
(2007/10/03)
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- Novel Insertion, Rearrangement and Addition Products from Dihalogenocarbene Reactions with 5(10)-Unsaturated Steroids
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Novel insertion, rearrangement and addition products from dibromocarbene and dichlorocarbene reactions with 5(10)-unsaturated steroids have been identified.The dihalogenocarbenes were prepared under phase-transfer conditions (CHBr3- or CHCl3-NaOH), and from CHBr3-KOBut-Et2O, phenyl(trichloromethyl)mercury and sodium trichloroacetate.Evidence that the major products arise from an initial dihalogenocarbene reaction on the α face of the molecule is reported.The major products obtained from addition of CBr2 to 3,17-disubstituted estr-5(10)-enes, after ketal hydrolysis, were 19(S)-bromo-9α,19-cyclo-10α-androst-4-en-3-one and 3',3',19(S)-tribromo-3'H-9α,19-cyclopropa-5β,10α-androstan-3-one derivatives together with the 19,19-dibromo-5α,19-cyclo-10α-steroid adduct.No products from addition of CBr2 to the β-face of the double bond, as previously reported, were identified.Reactions of CCl2 gave, besides rearrangement products analogous to those obtained from CBr2, a 5α-hydroxy-9α,19α-cycloandrostane derivative, the 9α-CHCl2 insertion derivative and both α- and β-face addition products to the double bond.Structures were established by homonuclear and heteronuclear correlation and nuclear Overhauser effect NMR measurements and X-ray crystallography.
- Templeton, John F.,Ling, Yangzhi,Lin, Weiyang,Pitura, Randy J.,Marat, Kirk,Bridson, John N.
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p. 1149 - 1158
(2007/10/02)
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