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filingDate 1971-07-06-04:00^^<http://www.w3.org/2001/XMLSchema#date>
publicationDate 1976-02-18-04:00^^<http://www.w3.org/2001/XMLSchema#date>
publicationNumber IE-35436-B1
titleOfInvention Cyclopentene derivatives and a process for the manufacture thereof
abstract 1336324 Cyclopentene derivatives F HOFFMANN-LA ROCHE & CO AG 8 July 1971 [10 July 1970] 32112/71 Heading C2C Novel cyclopentene derivatives of the formula wherein X is CH 3 CO, 1-hydroxyethyl, CH 3 CH 2 or CH 3 , and R<SP>1</SP> is CH 2 OH, alkoxymethylene, aralkoxymethylene, alkanoyloxymethylene, aroyloxymethylene, COOH, alkoxycarbonyl, aralkoxycarbonyl, carbamoyl, mono- or di- (C 1-6 alkyl)-carbamoyl, or a N-heterocyclylcarbonyl group attached to the polyene chain through the carbonyl group, are prepared by cyclizing - cum - dehydrating a 3,7,11,11 - tetramethyl - 10,15 - dioxo -'2,4,6,8 - hexadecatetraenoic acid or alkyl or aralkyl esters thereof, or by reacting phosphonium salts of the formula in which X<SP>11</SP> is CH 2 CO (the carbonyl group of which may be ketalized) or, CH 3 or CH 3 CH 2 , Y is aryl or di-(C 1-6 alkyl)amino and Z is a halogen or hydrosulphate ion with aldehydes of the formula or by reacting aldehydes of the formula with phosphonium salts of the formula and, in any desired sequence, subjecting if desired acids so obtained to esterification or to amidation or after ketalization of any keto group which may be present, to reduction and deketalization, or subjecting if desired esters so obtained to hydrolysis of amidation, or, after ketalization of any keto group which may be present to reduction and deketalization, and, if desired, etherifying alcohols thus obtained from acids or esters, and, if desired, reducing an acetyl group X to the 1-hydroxyethyl group or to the ethyl group. 9 - [2 - (1,1 - Ethylendioxyethyl)- 5,5 - dimethylcyclopent - 1 - enyl] - 3,7 - dimethyl - 2,4,6,8,- nonatetraenoic acid ethyl ester and butyl ester are obtained by reacting (3 - ethoxycarbonyl - 2- methylprop - 2 - enyl) - triphenylphosphonium chloride with 5 - [2 - (1,1 - ethylenedioxyethyl)- 5,5 - dimethylcyclopent - 1 - enyl] - 3 - methyl- 2,4-pentadien-1-al and by reacting {5-[2-(1,1- ethylenedioxy ethyl) - 5,5 - dimethylcyclopent- 1 - enyl] - 3 - methyl - 2,4 - pentadienyl} - triphenylphosphonium bromide with 3-formylcrotonic butyl ester respectively. The above ethyl ester may also be prepared by reacting 5 - [2 - (1,1 - ethylenedioxyethyl) - 5,5 - dimethylcyclopent - 1 - enyl] - 3 - methyl - 2,4 - pentadien - 1 - al, 4 - chloro - 3 - methylcrotonic acid ethyl ester and triphenyl phosphine. Pharmaceutical compositions, suitable for enteral, parenteral or topical administration, contain the above novel cyclopentene derivatives and compatible pharmaceutical carriers. The compounds are used in the treatment of precanceroses, carcinomas, acne and psoriasis.n[GB1336324A]
priorityDate 1970-07-10-04:00^^<http://www.w3.org/2001/XMLSchema#date>
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