Patent GB-1208342-A (GB)
Title: Cyclohexenyl compounds and process for preparing them
IPC: C07C45/67
Filed: 1968-01-22
Abstract: 1,208,342. Cyclohexenone derivatives. FARBWERKE HOECHST A.G. 22 Jan., 1968 [20 Jan., 1967], No. 3196/68. Heading C2C. Novel cyclohexenone derivatives of the general formula wherein n is 2, 3 or 4, R is hydrogen or methyl, R 1  is methyl or ethyl, the two symbols R having the same meaning and the two symbols R 1  having the same meaning, and R 2  is hydrogen or the two symbols R 2  together are a C-C linkage, and X is oxygen or (H 1 OH), are prepared by acetylation of a keto-alcohol of the general formula treatment of the resulting enol-acetate of the general formula wherein Ac is an acetyl radical, with bromine, followed by a lithium halide, optionally in the presence of an alkali metal carbonate, in a dialkylamide, alkaline hydrolysis of the resulting keto-acetate of the general formula and, when X is oxygen, the obtained alcohol is oxidized with a metal oxide. Pharmaceutical compositions having androgenic, gestagenic, antiphlogistic and anabolic activity comprise as active ingredient a cyclohexenone derivative of the first general formula above in admixture or conjunction with a pharmaceutically suitable carrier. 3 - (41 - Oxocycloheryl) - 4 - (3<SP>1</SP> - hydrozycyclohexyl)-hex-3-ene is prepared by reaction of 4- oxocyclohexane-carboxylic acid ethyl ester and pyrocatechol, condensation of the resulting 4,4- benzene - 1<SP>1</SP>,2<SP>1</SP> - dioxy - cyclohexane - carboxylic acid ethyl ester with 3-ethylenedioxy-cyclohexane-carboxylic acid ethyl ester in the presence of an alkali metal, followed by oxidation with chromium trioxide in pyridine, reaction of the resulting 1-(4<SP>1</SP>,4<SP>1</SP>-benzene-1<SP>11</SP>,2<SP>11</SP>-dioxycyclohexyl) - 2 - (3<SP>1</SP>,3<SP>1</SP> - ethylenedioxy) - cyclohexyl-dioxo-ethane with an acetylene-magnesium halide, treatment of the resulting 3-(4<SP>1</SP>,4<SP>1</SP>- benzene - 1<SP>11</SP>,2<SP>11</SP> - dioxycyclohexyl) - 4 - (31- ethylenedioxycyclohexyl)- hexa - 1,5 - diine - 3,4- diol with diphosphorus tetraiodide in the presence of carbon disulphide and a tertiary organic base, reduction of the resulting 3-(4<SP>1</SP>,4<SP>1</SP>- benzene - 1<SP>11</SP>,2<SP>11</SP> - dioxycyclohexyl) - 4 - (3<SP>1</SP>- ethylenedioxy - cyclohexyl) - hexa - 1,5 - diine - 3- ene with potassium azodicarboxylate, treatment of the resulting 3-(4<SP>1</SP>,4<SP>1</SP>-benzene-1<SP>11</SP>,2<SP>11</SP>-dioxycyclohexyl) - 4 - (3<SP>1</SP>,3<SP>1</SP> - ethylenedioxy) - hex - 3 - ene with sulphuric acid in acetone, reduction of the resulting 3 - (4<SP>1</SP>,4<SP>1</SP> - benzene - 1<SP>11</SP>,2<SP>11</SP> - dioxycyclohexyl) - 4 - (3<SP>1</SP>- oxocyclohexyl) - hex - 3 - ene with lithium aluminium hydride reduction of the obtained 3-(4<SP>1</SP>,4<SP>1</SP>-benzene-1<SP>11</SP>,2<SP>11</SP>-dioxycyclohexyl) - 4 - (3<SP>1 </SP>- hydroxycyclohexyl) - hex - 3 - ene with an alkali metal in ammonia in the presence of an alcohol and subsequent treatment with sulphuric acid in acetone. 2 - (1<SP>1</SP> - Methyl - 41 - oxocyclohexyl) - 3 - (1<SP>1</SP>- methyl - 3<SP>1</SP> - hydroxycyclohexyl) - but - 2 - ene is prepared by reaction of 1-(4<SP>1</SP>,4<SP>1</SP>-benzene-1<SP>11</SP>,2<SP>11</SP>- dioxycyclohexyl) - 2 - (3<SP>1</SP>,3<SP>1</SP> - ethylenedioxycyclohexyl)-dioxoethane with a methyl halide in the presence of a strong base, reaction of the resulting 1 - (1<SP>1</SP> - methyl - 4<SP>1</SP>,4<SP>1</SP> - benzene - 1<SP>11</SP>,2<SP>11</SP>- dioxycyclohexyl) - 2 - (1<SP>1</SP> - methyl - 3<SP>1</SP>,3<SP>1</SP> - ethylenedioxy-cyclohexyl)-dioxoethane with a methyl magnesium halide, treatment of the mixture of ketoalcohols obtained of the formulµ with a dehydrating agent, treatment of the mixture of unsaturated ketones obtained of the formulµ with lithium-methyl, dehydration of the mixture of unsaturated alcohols, obtained of the formulµ treatment of the resulting diene of the formula with an alkali metal in liquid ammonia followed by sulphuric acid in acetone, reaction of the resulting 2 - (11 - methyl - 41 - oxocyclohexyl) - 3- (1<SP>1</SP> - methyl - 3<SP>1</SP> - oxo - cyclohexyl) - but - 2 - ene with 2,3-butanediol, reduction of the resulting monoketal-ketone with lithium aluminium hydride and treatment of the obtained monoketalalcohol with sulphuric acid in acetone.