Verfahren zur Herstellung von aethylenischen Carbonylverbindungen

摘要

1,204,754. Ethylenic carbonyl compounds. RHONE-POULENC S.A. 27 Nov., 1968 [28 Nov., 1967], No. 56380/68. Heading C2C. [Also in Division C1] Ethylenic carbonyl compounds (aldehydes and ketones) are prepared by isomerizing by heating an acetylenic alcohol of formula where R1, R2 and R3 are independently H, saturated or unsaturated aliphatic or cycloaliphatic radicals or aromatic or arylaliphatic radicals, either substituted or unsubstituted, or R1 and R2 may be linked together, in the liquid phase in the presence of a catalyst based on a transition metal of Groups V, VI or VII of the Periodic Table, specifically V, Nb, Mo, W or Re. The catalysts may be salts of inorganic or organic acids, salts or esters of acids derived from the specified metals, chelates or co-ordination complexes or metal alkyls. The products are generally of formula but where R1 and R2 are linked, a #-ethylenic carbonyl compound with an intracyclic double bond is also formed. Examples prepare citral; 3,7,11 - trimethyldodeca - 2,6,10 - trienal; 4,7- dimethyl - 3 - ethyl -, 3 - methyl - 3 - isobutyl -, 7 - methyl - 3 - ethyl -, 3,7 - dimethyl - 4 - ethyl -, 7 - methyl - 3 - propyl -, 3,4,4,7 - tetramethyl - and 7 - methyl - 3 - isopropyl - 2,6 - octadienal; 3 - methyl - 2 - nonenal; 2,2,6 - trimethylcyclohexylidene -, (2,6,6 - trimethylcyclohexen - 1 - yl) -, 2 - (3 - methyl - 2 - buten- 1 - yl) - cyclohexylidene - and [6 - (3 - methyl - 2 - buten - 1 - yl) - cyclohexen - 1 - yl] - acetaldehyde; 2 - methyl - 2 - nonen - 4 - one; 2 - octen - 4 - one; and 4 - phenyl - 2 - methyl - 2 - buten - 4-one. Catalysts prepared include various lower alkyl, cyclohexyl, dehydrolinalyl and tetrahydrolinalyl orthovanadates; propyl molybdate; ethyl, 1,1-dimethylpropyl, cyclohexyl and butyl orthotungstates; vanadyl acetate, hexahydrobenzoate, benzoate and stearate; vanadyl acetylacetonate; and the reaction product of MoO 3 and acetylacetone. A mixture of citral and dehydrolinalool obtained from dehydrolinalool according to the above process is reacted with acetone and NaOH to give pseudo-ionone and this is treated with H 2 SO 4 to give #-ionone.