TOTAL PROCESS FOR MAKING 13-HYDROCARBON SUBSTITUTED GONAPOLYENE - 17 - ONE COMPOUNDS AND INTERMEDIATES PRODUCED IN THE COURSE OF THE PROCESS

摘要

1,234,076. 13 - (Hydrocarbon substituted)- gonapolyen - 17 - ones and -17# - ols. TAKEDA YAKUHIN KOGYO K.K. 22 May, 1968 [24 May, 1967; 25 May, 1967], No. 24345/68. Heading C2C and C2U. A novel process comprises reacting a 2-(1SP1/SP- hydroxy - 1SP1/SP - tetralino) - ethylene or S - [2- (1SP1/SP - tetraliden) - ethyl] - thiuronium compound with a 4 - (hydroxy or acyloxyl) - 2 - (hydrocarbon substituted) - cyclopentane - 1,3 - dione to produce a 13 - (hydrocarbon substituted) - 8,14 - secogona - 1,3,5(10),9(11),15 - pentaene- 14,17 - dione, reducing this to the corresponding 17#-ol, acylating this to give the 17-acylate, reacting this with an alcohol, phenol or fatty acid or mixture thereof in the presence of an acid catalyst to give a 16# - (etherified or esterified hydroxy) - 17# - acyloxy - 13 - (hydrocarbon substituted) - gona - 1,3,5(10),8,14 - pentaene (said 16 - esterifying or -etherifying group being derived from said alcohol, phenol or fatty acid, or from said mixture to give a mixture of products), selectively reducing the #SP14/SP double bond, directly or after hydrolysis in the 17 - position, to give the corresponding gona - 1,3,5(10),8- tetraene, optionally reducing this to the corresponding gona-1,3,5(10)-triene or gona-2,5(10)- diene, and contacting the di-, tri- or tetra-ene, after 17 - acylation if desired, with an acid reagent to give a corresponding 16-unsubstituted - 13 - (hydrocarbon substituted) - 17- keto-gona-(tetra-, tri- or di-ene). These reactions may be carried out using optically active compounds or racemates, which may contain additional substituents. Novel intermediates are 3,16 - dimethoxyestra - 1,3,5(10),8,14 - pentaen- 17# - ol and its benzoate and the corresponding 1,3,5(10),8 - tetraenes, and 3,16 - dimethoxyestra - 1,3,5(10) - trien - 17# - ol, all these compounds being racemates.