FI45320B

1,265,393. 1α,2α - Methylene - steroids. SCHERING A.G. 31 March, 1969 [5 April, 1968], No. 16626/69. Heading C2U. Novel steroids of the formula (where R is CH 3 or C 2 H 5 and R1 is C i _ 4 alkyl or tetrahydropyranyl) are prepared by introducing a double bond into the corresponding ring-A- saturated steroids (this method is only used when R1 is C 1-4 alkyl) or by etherifying the corresponding 17#-ols with dihydropyran or an alkylating agent. Introduction of a A4-double bond may be effected chemically or microbiologically. One method of chemical introduction is as follows This involves 3-enol-acetylation, halogenation (bromination is depicted) and dehydrohalogenation. 17# - Hydroxy - 18 - methyl - 1α,2α - methylene- A4 - estren 3 - one is prepared from 17#- hydroxy - 18 - methyl - D4 - estren - 3 - one via 17# - hydroxy - 18 - methyl - 5α - estran - 3- one, 17# - acetoxy - 18 - methyl 5α - estran - 3- one, the bromo-derivative of the last-mentioned compound, 17# - acetoxy - 18 - methyl - 5α- estr - 1 - en - 3 - one, 17# - acetoxy - 18 - methyl- 1α,2α - methylene - 5α - estran - 3 - one, the 3- enol acetate of the last-named, 17#-acetoxy-4- bromo - 18 - methyl - 1α,2α - methylene - 5α - estran - 3 - one and 17# - acetoxy - 18 - methyl- 1α,2α - methylene - A4 - estren - 3 - one. The novel 17# - methoxy - 18 methyl - 1α,2α - methylene - 5α - estran - 3 - one is prepared by methylation of the novel 17# - hydroxy - 18 - methyl- 1α,2α - methylene - 5α . estran - 3 - one, in turn prepared by hydrolysis of its 17-acetate. The novel 17# - methoxy - 1α,2α - methylene - 5α- estran - 3 - one is prepared by methyleneation of 17# - methoxy - 5α - estr - 1 - en - 3 - one, in turn prepared from 17#-hydroxy-5α-estran-3-one via 1 7#-methoxy-5α-estran-3-one and its bromo derivative. The novel steroids of the first general formula above are stated to be anabolic agents, and they may be made up into pharmaceutical compositions with suitable carriers. Specifications 1,239,479 and 1,105,999 are referred to