Synthesis and Structures of 6-Aryl-1,5-dimethoxycarbonyl-2-methyl-4-morpholino-1,3-cyclohexadienes and Related Compounds

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Reaction of benzaldehyde (1a) with methyl acetoacetate (2) in the presence of morpholine (or piperidine) and AcOH in refluxing C_6H_6 yielded a new condensation product, 1,5-dimethoxycarbonyl-2-methyl-4-morpholino (or piperidino)-6-phenyl-1,3-cyclohexadiene (3a or 10a), along with a usual product, benzylideneacetoacetate (4a). Under the conditions determined as optimum, 3a was prepared in 86% yield. However, reaction of 1a and 2 in the presence of morpholine (or piperidine) in EtOH solution yielded 4a, a poly-substituted cyclohexanone derivative (5a) and a cyclohexenone derivative (7a), while the production of 3a was not detected. Compound 3a (or 10a) was also prepared by an alternative procedure of condensation of 5a or 6a with morpholine (or piperidine) in the presence of TiCl_4. Compound 6a was prepared by dehydration of 5a under acidic conditions. Acid hydrolysis of 3a afforded 6'a, which is the C-4 epimer of 6a. The configurations of 3a, 6a and 6'a were assigned on the basis of the proton nuclear magnetic resonance (^1H-NMR) spectra. Mechanisms of the formation of 3a are discussed. Some of 3 and related compounds exhibited potent calcium channel-blocking activity.
社団法人日本薬学会の論文
1992-04-25