17-11-1971 дата публикации
Номер: GB1253925A
Автор:
1,253,925. 5,10 - Seco - 5,10 - (methylene, dihalomethylene or oxa)steroids. SYNTEX CORP. 12 Feb., 1969 [18 March, 1968], No. 7613/96. Headings C2C and C2U. Novel compounds of the formulµ (wherein X is CH 2 , CF 2 , CCl 2 or O; R is H, acyloxy, C 1-6 alkoxy, cyclopentyloxy, -cyclohexyloxy, tetrahydropyranyloxy or tetrahydrofuranyloxy; R<SP>1</SP> is CH 3 or C 2 H 5 ; R<SP>2</SP> is OH, acyloxy, tetrahydropyranyloxy or tetrahydrofuranyloxy; and R<SP>3</SP> is H, alkyl, alkenyl, alkynyl, haloalkynyl, cyclopropyl, dichloro- or difluorocyclopropyl, propadienyl, or dichloro- or difluoro-cyclopropenyl; or R<SP>2</SP>+R<SP>3</SP> is =O; R<SP>11</SP> is C 1-6 alkyl, cyclopentyl, cyclohexyl, acyl, tetrahydropyranyl or tetrahydrofuranyl; and X<SP>1</SP> is CH 2 , CF 2 or CCl 2 ) are prepared by the following reaction sequences (I) # (II) is effected with an alkali metal in liquid ammonia, (II) # (III) is effected with a per-acid to give (III) wherein X is O, or with a dihalocarbene generated from sodium trichloroacetate or chlorodifluoroacetate to give (III) wherein X is CCl 2 and CF 2 , respectively, (III) wherein X is CH 2 being prepared by treatment of the 5,10-dichloromethylene compound with Na or Li in 1.NH 3 and a lower alcohol or with LiAlH 4 , (IV) # (V) is effected with a base, e.g. an alkali metal hydroxide or alkoxide; (R<SP>1</SP> is C 1-6 alkyl). (VI) # (VII) is effected with cupric bromide, and the subsequent dehydrobromination by treatment with an alkali halide and alkali or alkaline earth metal carbonate or bicarbonate; (VIII) # (IX)is enolacylation or enol-alkylation and the products may be converted to the corresponding tetrahydropyranyl and tetrahydrofuranyl ethers by standard procedures. (IX) # (X) is effected directly using a Pd catalyst, 2,3-dichloro-5,6- dicyano - 1,4 - benzoquinone or N - bromosuccinimide or indirectly via a 7,8-dibromo derivative; (VI<SP ...
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