A method for the production of deasteroiden

摘要

1374850 De-A-steroids, 4,5-secosteroids F HOFFMANN-LA ROCHE & CO AG 10 Nov 1972 [12 Nov 1971] 52027/72 Heading C2C The invention relates to compounds of formula wherein RSP1/SP is 3-oxobutyl, ketalized 3-oxobutyl, 3-chloro-2-butenyl, 3-methyl-2-butenyl, 3- (C 1 -C 6 alkoxy)-2-butenyl, 3-hydroxybutyl (or an ester or ether thereof), 2-carboxyethyl, 2-cyanoethyl, 2-(C 2 -C 6 alkoxycarbonyl)-ethyl or a 4-isoxazolylmethyl group bearing a C 1 -C 6 alkyl substituent in at least one of positions 3 and 5; and D is a group of formula wherein m is 1 or 2; RSP2/SP is free, esterified or etherified hydroxy; RSP3/SP is H, C 1 -C 6 alkyl or C 2 -C 6 alkynyl; or RSP2/SP and RSP3/SP together represent a ketal, ethylidene, 1-(C 1 -C 6 alkanoyloxy)- ethylidene or bis-(methylenedioxy)ethyl group; RSP4/SP is H or OH; RSP5/SP is oxo, ketal, (H, OH), (H, esterified OH) or (H, etherified OH); RSP6/SP is H or free, esterified or etherified OH; or RSP4/SP and RSP6/SP may together represent C 1 -C 6 alkylidenedioxy when RSP5/SP is oxo; and RSP7/SP is H or Me. The invention comprises (A) compounds I (with the exception of those in which, simultaneously, m is 1; RSP1/SP is 3-oxobutyl, ketalized 3-oxobutyl or 3-chloro-2-butenyl; RSP2/SP is esterified hydroxy; and RSP3/SP is H); and (B) the preparation of compounds I by methylating the corresponding #SP9(10)/SP-10-demethyl compounds (steroid numbering) below - 50‹ C. The minor proportion of 10x-methyl epimer also formed may be removed from the 10#-methyl product by chromatography. Any ketal groups in the product may be hydrolysed.