Patent GB-1306244-A (GB)
IPC: C07C37/00
Filed: 1970-08-24
Abstract: 1306244 1,1 - Diaryl - 2 - adamantyl - ethylenes; phosphonium compounds SCHERICO Ltd 24 Aug 1970 [25 Aug 1969] 40589/70 Headings C2C and C2P Novel 1,1 - diaryl - 2 - adamantyl - ethylenes of the general formula wherein Ad is an adamantyl group, each A is independently a hydrogen or halogen atom or an alkyl group and each R is independently a free, esterified or etherified hydroxy group, are prepared (a) by subjection of a 1,1-diaryl-2-adamantyl-ethane of the general formula wherein X and Y are radicals which are capable of being eliminated under the reaction conditions, to an elimination reaction leading to the removal of X and Y and the formation of a double bond between the carbon atoms to which they are attached; (b) by condensation of a 1-aryl-2- adamantyl-ethylene and a benzene compound of the respective general formulµ wherein U and V are reactive radicals capable of being eliminated under the reaction conditions; (c) by condensation of a 1,1-diarylethylene of the general formula with an adamantane of the general formula Ad-V; (d) by condensation of a diarylmethane and an adamantylmethane of the respective general formulµ and (e) by reduction of the corresponding compound having an additional -S- linkage between the o- and o<SP>1</SP>-positions of the aryl substituents with elimination of hydrogen sulphide; followed optionally by esterification of free hydroxy groups in the product, or saponification or ether-cleavage of esterified or etherified hydroxy groups, respectively, in the product. Di - (p - methoxyphenyl) - methyl 1 - adamantyl ketone is prepared by reaction of the imidazolide of 1 -adamantane-carboxylic acid with a Grignard reagent prepared from magnesium and di- (p-methoxyphenyl)-methyl bromide in dry tetrahydrofuran, followed by treatment with hydrochloric acid. Di-(p-methoxyphenyl)-methyl 2-adamantyl ketone is prepared by lithium aluminium hydride reduction of the imidazolide of 2-adamantane-carboxylic acid, reaction of the resulting adamantane-2-carboxaldehyde with 1,2- ethanedithiol in the presence of hydrogen chloride and treatment of the resulting dithioacetal with n-butyl lithium in hexane, followed by di - (p - methoxyphenyl) - methyl bromide in dry tetrahydrofuran. 1-Mercapto- 1,1-di-(phydroxyphenyl) - 2 - (1 - adamantyl) - ethane is prepared by reaction of 1,1-di-(p-hydroxy. phenyl) - 2 - (1 - adamantyl) - ethane with N- bromo-succinimide and reaction of the resulting 1 - bromo - 1,1 - di - (p - hydroxyphenyl) - 2 - (1) adamantyl)-ethane with hydrogen sulphide. Ethyl 2,2 - di - (p - hydroxyphenyl) - 3 - hydroxy- 3-(1-adamantyl)-propionate is prepared by reaction of ethyl di-(p- 1 -ethoxyethoxyphenyl)- acetate with adamantane-1-carboxaldehyde in the presence of sodium methoxide. 1-Chlorosulphito - 1,1 - di - (p - methoxyphenyl) - 2 - (1- adamantyl)-ethane is prepared by treatment of methyl 1-adamantyl-acetate with a Grignard reagent prepared from magnesium and p-bromoanisole in dry ether, followed by water, and reaction of the resulting 1-hydroxy-1,1-di-(pmethoxyphenyl) - 2 - (1 - adamantyl) - ethane with thionyl chloride. 1-Iodo-1-p-methoxyphenyl-2-(1-adamantyl)-ethylene is prepared by reaction of 1 -p-methoxyphenyl-2-(1-adamantyl)- ethane with N-bromosuccinimide, reaction of the resulting 1,1 - dibromo - 1 - p - methoxyphenyl - 2 - (1 - adamantyl) - ethane with sodium iodide and treatment of the resulting 1,1-diiodo - 1 - p - methoxyphenyl - 2 - (1 - adamantyl)- ethane with sodium carbonate. 3,6-Dimethoxy- 9 - thiaxanthenyl - 1 - adamantyl - methqne is prepared by reaction of 3,6-dimethoxythiaxanthene with butyl lithium in dry tetrahydrofuran and then adamantane-1-carboxaldehyde, followed by treatment with thionyl chloride and then sodium hydroxide. 1,1-Di-(p-hydroxyphenyl) - 2 - (1 - adamantyl) - ethane is prepared by reaction of phenol and 1-adamantane-acetaldehyde in the presence of concentrated sulphuric acid. 1 -Adamantylmethyltriphenylphosphonium bromide is prepared by reaction of triphenylphosphine with 1-adamantylmethyl bromide. p,p<SP>1</SP> - Dimethoxybenzhydryltriphenylphosphonium bromide is prepared by reaction of triphenylphosphine with p,p<SP>1</SP>-dimethoxybenzhydryl bromide. Pharmaceutical compositions capable of inhibiting gestation in female mammals comprise, as active ingredient, a 1,1-diaryl-2-adamantylethylene of the first general formula above, in admixture with a suitable carrier or excipient, and may be administered orally or parenterally.