| 摘要 |
1,231,296. 19-Nor-steroids. MERK PATENT G.m.b.H. 28 Aug., 1969 [25 Oct., 1968], No. 42812/69. Heading C2U. [Also in Division A5] 19 - Nor - 3 - keto - #<SP>4</SP> - steroids are prepared by reacting 19-hydroxy-3-keto-#<SP>4</SP>-steroids with secondary amines to give 19-nor-3-enamines (3,5-dienes) and hydrolysing these. Further standard conversions can be carried out on the enamine at other parts of the molecule before hydrolysis, or hydrolysis may accompany such conversions. Specified conversions are: reduction of an 11-, 16-, 17- or 20-oxo group to two hydrogen atoms or to a hydroxy group; (ii) conversion of an 11-, 16-, 17- or 20-oxo group to an group where R is C 1-8 alkyl, C 2-4 alkenyl or C 2-4 alkynyl; (iii) conversion of a 16α,17α- epoxy - 16# - methyl - 17# - acetyl grouping to a 16-methylene-17α-(hydroxy or acyloxy)-17#- acetyl grouping; (iv) introduction of a #- ethoxycarbonylethyl or #-cyanoethyl group in the 4-position; and (v) introduction of an acetyl or propionyl group in the 4- or 6-position. 19 - Hydroxy - 4 - androstene - 3,16 - dione (XI) is prepared from 3#-acetoxy-5-androsten- 16-one (X) by the sequence X#3#-acetoxy- 5α - chloro - 6# - hydroxyandrostan - 16 - one #3# - acetoxy - 5α - chloro - 6#,19 - epoxyandrostan - 16 - one#5α - chloro - 6#,19-epoxyandrostane - 3,16 - dione#6#,19 - epoxy - 4 - androstene- 3,16-dione#XI. 16α,17α - Epoxy - 16# - methyl - 19 - hydroxy- 4-pregnene-3,20-dione (XIV) is prepared from 3# - acetoxy - 16α,17α - epoxy - 16# - methyl- 5-pregnen-20-one (XIII) by the sequence XIII#3# - acetoxy - 5α - bromo - 6# - hydroxy- 16α,17α - epoxy - 16# - methylpregnan - 20 - one #3# - acetoxy - 5α - bromo - 6#,19; 16α,17α- diepoxy - 16# - methylpregnan - 20 - one#3#- acetoxy - 6#,19; 16α,17α - diepoxy - 16# - methyl- 4 - pregnen - 20 - one#3# - hydroxy - 6#,19; 16α,17α - diepoxy - 16# - methyl - 4 - pregnen- 20 - one#6#,19; 16α,17α - diepoxy - 16#- methyl - 4 - pregnene - 3,20 - dione#XIV |
