| 摘要 |
22 The present invention relates to a method for the synthesis of .alpha., .beta.-unsaturated ketones which comprises, in the method for the synthesis of .alpha., .beta.-unsaturated ketones represented by generale formula R1.CH=CH-C-CH3 0 (where R1 is an aliphatic group with a side chain at the 1 position, an alicyclic group, a substituted alicyclic group, a heterocyclic group, a substituted heterocyclic group, a phenyl group or a substituted phenyl group), reacting aldehydes represented by general formula R1CHO (where R1 is as defined above) with alkali metal salt of acetoacetic acid represented by general formula (where M ? is an alkali metal ion), in the presence as a catalyst of 3-azabicyclo¢3. 2,2! nonane, a cyclic secondary amine represented by general formula (1) (1) (where n is 3 or more and up to 5, m is 1 or more and up to 10, R2 is an alkyl group having 1 to 10 carbon atoms and of straight chain or with side chains, an alkyl group substituted by alicyclic groups or phenyl groups, an alcyclic group which may be substituted by lower alkyl groups, or a phenyl group which may be substituted by lower alkyl groups, and an R2 substitution position is at a carbon atom other than two those adjacent to N), a cyclic secondary amine represented by general formula (2) 23 (2) (where, ? is 1 or more and up to 6, a ring with N is a 6-membered, 7-membered or 8membered ring, the two neighbors of N are methylene, R3 is a lower alkyl group, its substitution position is at a carbon atom other than two those adjacent to N. and is an alicyclic group or a phenyl group), or a secondary amine represented by general formula (3) CH3NHCH2R4 (3) (where R4 is an aliphatic group having 5 to 17 carbon atoms and of straight chain or with side chains, an alicyclic group which may be substituted by lower alkyl groups. a phenyl group which may be substituted by lower alkyl groups, or an alkyl groupsubstituted by phenyl groups), in a mixuture solvent of water and water-insoluble organic solvent, while keeping the pH constant with mineral acid, and by adjusting an amount of water.
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