BICYCLOHEPTENE DERIVATIVES

摘要

1353922 Norbornene derivatives IMPERIAL CHEMICAL INDUSTRIES Ltd 28 March 1972 [13 April 1971 16 Dec 1971] 9223/71 and 58400/71 Heading C2C The inventions comprises norbornene-7-sync-arbaldehydes and 7-(substituted-methylene)- norbornenes of the formulae wherein R1 is halogen, R2 is CN, CONH 2 , G 2-6 alkoxycarbonyl or N-(C 1-6 alkyl) carbamoyl, and in the 7-(substituted-methylene)norbornenes R2 may also be chloroformyl, P and R3 is alkyl, alkanoyl, alkanesulphonyl or arenesulphonyl, their preparation and the preparation of prostaglandins which includes the step of preparing the norbornene-7-syn-carbaldehydes. The norbornene-7-syn-carbaldehydes are prepared by the acid hydrolysis of the corresponding 7-(substituted-methylene)norbornenes of the above formula, obtained by reacting of ulvene derivatives of the formula with compounds of the formula CH 2 = CR1R2, so that the initially formed norbornene-7-anticarbaldehydes are isomerized to the corresponding norbornenc-7-syn-carbaldehyde without substantial decomposition. The following intermediates are prepared: 5 - chloro - 7 - syn - formyl - 2 - norbornene - 7- carbonitrile dimethyl acetal and cyclic acetal with o-hydroxymethylbenzyl alcohol, 7-synformyl-2-norbonen-5-one cyclic acetal with ohydroxymethylbenzyl alcohol and dimethyl acetal, the cyclic acetal with o-hydroxymethylbenzyl alcohol of 5-formyl-4-hydroxy-2-cyclopentene-1-acetic acid γ-lactone, 4#-formyl-5α- hydroxy - 6# - iodo - 3,3aα,4,5,6,6aα - hexahydro-2H-cyclopenta(b)furan-2-one dimethyl acetal and cyclic acetal with o-hydroxymethylbenzyl alcohol, 4#-formyl-6#-iodo-5a-(p-phenylbenzoyloxy) - 3,3aα,4,5,6,6aα - hexahydro - 2H- cyclopenta(b)furan-2-one, dimethyl acetal and cyclic acetal with o-hydroxymethylbenzyl alcohol, 4#-formyl-5α-(p-phenylbenzoyloxy)-3,3aα, 4,5,6,6aα - hexahydro - 2H - cylcopenta[b]furan- 2-one and its dimethyl acetal and cyclic acetal with o-hydroxymethylbenzyl alcohol, the Schiff base obtained from 5-chloro-7-anti-formyl-2- norbomene-7-carbonitrile and p-chloroaniline, 5 - chloro - 7 - anti - formyl - 2 - norbornene - 5- carboxamide, methyl 5-chloro-7-anti-formyl-2- norborne-5-carboxylate, and 5-chloro-7-syn-(dimethoxymethyl)-2-norbomene-5-carboxamide.