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http://rdf.ncbi.nlm.nih.gov/pubchem/patentipc/C07J75-00
filingDate 1969-06-20-04:00^^<http://www.w3.org/2001/XMLSchema#date>
publicationDate 1973-05-16-04:00^^<http://www.w3.org/2001/XMLSchema#date>
publicationNumber GB-1317185-A
titleOfInvention Acyloxy-3alpha-hydroxy-pregnones
abstract 1317185 21 - Acyloxy - 3α - hydroxy - 5α- pregnane-11,20-diones GLAXO LABORATORIES Ltd 11 June 1970 [20 June 1969] 33162/72 Divided out of 1317184 Heading C2U [Also in Division C3] Novel steroids of the formula (wherein R is optionally substituted alkanoyl, aroyl or aralkanoyl) are prepared (i) by reacting lead tetraacylates with 3α-hydroxy-5α-pregnane-11,20-dione in which the OH group may be protected; (ii) by reduction of a 21-acyloxy- 5α - pregnane - 3,11,20 - trione, e.g. using Saccharomyces cerevisiae; (iii) by reacting 21- halo - 5α - pregnan - 3α - ol - 11,20 - diones (prepared by halogenation of the 21-unsubstituted compound) with a salt of the appropriate acid; or (iv) by hydrolysing a product of (i) above containing a protected 3-hydroxy group to the corresponding 21 -ol, acylating this and removing the protecting group. 3α - Trimethylsilyloxy - 5α - pregnane - 11,20- dione and 3α - (2,2,2 - trichloroethoxycarbonyloxy)-5α-pregnane-11,20-dione are prepared from the 3a-ol and trimethylchlorosilane and 2,2,2- trichloroethyl chloroformate respectively. They are subsequently converted to their 21-acetoxy derivatives as described in (i) above. 17a - Bromo - 5α - pregnan - 3α - ol - 11,20- dione is a by-product in the 21-bromination of 5α-pregnan-3α-ol-11,20-dione. Specified intermediates in process (iv) are 21 - acetoxy - 5α - pregnan - 3α - ol - 11,20 - dione 3-nitrate and the corresponding 21-isobutyryloxy and hemisuccinoyloxy compounds and 5α-pregnane - 3α, 21 - diol - 11,20 - dione 3 - nitrate.
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