Neue Phenanthren-2-carbonsaeuren und Verfahren zu ihrer Herstellung

摘要

1,234,282. 8,14 - Seco - 16 - oxa - steroids. SYNTEX CORP. 9 May, 1968 [15 May, 1967; 25 Sept., 1967], No. 2121/71. Divided out of 1,234,281. Heading C2C. The invention comprises compounds of Formula (III) wherein R1 is H, OH, C 1-6 alkoxy, cyclopentyloxy, cyclohexyloxy, tetrahydropyran - 2 - yloxy, tetrahydrofuran - 2 - yloxy or C 1-6 hydrocarbon carboxylic acyloxy; R2 has any value defined for R1 or is C 1-6 alkyl; R3 is H, Me or Et; R4 is H, Me, Et, Pr, Pri , Ph, benzyl, C 1-6 alkoxy, or CN; and R5 is H, Me, Et, Pr or Pri; with the proviso that when R1 is alkoxy, at least one of R2, R3 and R5 is other than H. These compounds are prepared by reacting a compound of Formula (II) either with an appropriate 1 - vinyl - 1 - tetralol under alkaline conditions or with a salt of Formula (I) (wherein Ac is acetyl). Compounds of Formula (I) are prepared by the action of isothiourea and acetic acid on the corresponding 1 - vinyl - 1 - tetralols, the latter being prepared by the action of vinyl magnesium bromide on the corresponding 1 - tetralones, the latter in turn being prepared by cyclization of the corresponding 4 - phenylbutanoic acids. Compounds of Formula (II) wherein R4 is Me, Et, Pr or Pri and R5 is Me, Et or Pri are prepared from compounds of formula by reaction with Br 2 . Compounds of Formula (II) wherein R4 is CN and R5 is H, Me, Et, Pr or Pri are prepared from compounds of formula by reaction with Br 2 . Methyl 2 - cyano - 3 - oxovalerate is prepared by reacting methyl cyanoacetate with propionyl chloride and sodium. 3 - (3,5 - Dimethoxybenzyl)butanoic acid (XX) is prepared from 3,5 - dimethoxybenzoic acid (XXI) by the sequence: XXI#3,5 - dimethoxybenzoyl chloride#3,5 - dimethoxypropiophenone#3 - (3,5 - dimethoxybenzoyl)- 2 - butenoic acid#3 - (3,5 - dimethoxybenzoyl)-butanoic acid#XX.