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摘要

1468402 Triarylphosphonium salts F HOFFMANNLA ROCHE & CO AG 29 March 1974 [30 March 1973] Divided out of 1468401 09185/76 Heading C2P The invention comprises triaryl phosphonium salts of the general formula wherein R 1 and R 2 each represent a lower alkyl group, R 3 represents a hydrogen or halogen atom or a lower alkyl, lower alkoxy, lower alkenoxy, nitro, amino, mono(lower alkyl)- amino, di(lower alkyl)amino, lower alkanoylamino or N-heterocyclic group, R 4 represents a lower alkenyl, lower alkoxy, lower alkenoxy, nitro, amino, mono(lower alkyl)amino, di(lower alkyl)amino, lower alkanoylamino or N-heterocyclic group and R 5 represents a hydrogen or halogen atom or a lower alkyl, lower alkenyl, lower alkoxy, lower alkenoxy, nitro, amino, mono(lower alkyl)amino, di(lower alkul)amino, lower alkanoylamino or N-heterocyclic group provided that when R 3 or R 5 is a halogen atom R 4 is other than a lower alkoxy group, m is 0 or 1, X is aryl and Y is the anion of an organic or inorganic acid, the lower alkyl, lower alkenyl, lower alkoxy, lower alkenoxy, and lower alkanoyl groups being defined as those containing up to 6 carbon atoms in each case. The aryl group X includes C 1 -C 6 alkylphenyl and C 1 - C 6 alkoxyphenyl and the preferred anions Y are Cl, Br, I, hydrosulphate and tosyloxy. Specified N-heterocyclic groups are pyrrolidino, piperidino, morpholino and thiamorpholino. The compounds in which m is zero and Y is a halide anion may be obtained by treating a corresponding (R 1 -R 5 )-benzene with formaldehyde in the presence of a hydrohalic acid, e.g. cone. HCI, if desired in a solvent and reacting the resulting (R 1 -R 5 )-benzyl halide with a triaryl phosphine in a solvent. Compounds in which m is 1 and Y is a halide anion can be obtained by reacting a formylating agent with the corresponding (R 1 - R 5 )-benzene, e.g. by reaction with orthoformic acid, formyl chloride or dimethyl formamide in the presence of a Lewis acid, reacting the resulting (R 1 -R 5 )-benzaldehyde with acetone in the presence of alkali to form a 4-(R 1 -R 5 )-phenylbut-3-en-2-one, converting the latter to the corresponding acetylenic alcohol (5-(R 1 -R 5 )- phenyl - 3 - methyl - 3 - hydroxy - penta - 4 - en- 1-yne) by a Grignard reaction with addition of acetylene, partially hydrogenating the acetylenic alcohol to form the corresponding diolefinic alcohol and then converting the latter to a triarylphosphonium salt by treating with a triaryl phosphine in the presence of a hydrohalide, e.g. HCl or HBr, in a solvent, e.g. benzene. The products are useful as intermediates in the production of polyene derivatives having therapeutic properties.