Studies on Structure-Activity Relationship of Analgetics. XVII. Syntheses of Homobenzomorphans and Related Compounds.(2)

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概要

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• New synthetic routes of 3-methyl-2,3,4,5,6,7-hexahydro-2,7-methano-1H-3-benzazonine (A) and 4-methyl-2,3,4,5,6,7-hexahydro-1,6-methano-1H-4-benzazonine (B) were described. A Schmidt reaction of ethyl 2-oxo-5-phenylcyclohexanecarboxylate (I) gave the corresponding lactam (II), which in turn was reduced with lithium aluminum hydride to afford 2-hydroxymethyl-4-phenyl-2,3,4,5,6,7-hexahydro-1H-azepioe (III). The N-ben-zoyl derivative (IV) of III was oxidized with dimethylsulfoxide and dicyclohexylcar-bodiimide to give the corresponding aldehyde (V), which was submitted to oxidation with silver hydrodde to give N-benzoyl-4-phenyl-2,3,4,5,6,7-hexahydro-1H-azepine-2-carboxylic acid (VI). Cyclization of VI by heating with polyphosphoric acid yielded 2,3,-4,5-tetrahydro-2,7-methano-1H-3-benzazonin-7(6H)-one (VII). A Wolff-Kishner reduction and the successive N-methylation gave the final compound A. While, Wolff-Kishner reduction of the N-methyl derivative (IX) of VII gave an elimination product, 1-(N-methylaminopropyl)-1,2-dihydronaphthalene (XI) . Treatment of 4-(N, N-dimethylaminoethyl)-3,4-dihydronaphthalen-1(2H)-one (XII) with ethyl chlorocarbonate afforded a carbamate, 4-(N-methyl-N-ethoaycarbonylaminoethyl)-3,4-dihydro-naphthalen-1(2H)-one (XIII), which was hydrolized, followed by a Mannich reaction with formaldehyde to yield 4-methyl-2,3,4,5-tetrahydro-1,6-methano-1H-4-benzazonin-7(6H)-one (XV). Reduction of the ketone XV with lithium aluminum hydride or by catalytic hydrogenation over Adams' catalyst gave the corresponding hydroxyl derivative (XVI), which was reduced with hydriodic acid and red phosphorus to give the final compound B.

• 公益社団法人日本薬学会の論文
• 1973-05-25

著者

• 米谷 正

  富山工業高等専門学校

• 塩谷 俊作

  Toyama Technical College

• 塩谷 俊作

  College Of Liberal Arts University Of Toyama

• 塩谷 俊作

  Toyama National College Of Technology

• 米谷 正

  Toyama Technical College

関連論文

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• On the Condensation Products of Nitromalondialdehyde with Ethylenediamine
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