Studies on Structure-Activity Relationship of Analgetics. XIII. Syntheses of Homobenzomorphans and Related Compounds. (1)

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概要

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• Synthetic routes of 3-methyl-2,3,4,5,6,7-hexahydro-2,7-methano-1H-3-benzazonine (X-A), 4-methyl-2,3,4,5,6,7-hexahydro-1,6-methano-1H-4-benzazonine (X-B) and 2-methyl-2,3,4,5,6,7-hexahydro-1,6-methano-1H-2-benzazonine (XX) having a new ring system were described. 4-Phenylcyclohexanone (I) was condensed with diethyl oxalate followed by decarbonylation to give ethyl 2-oxo-5-phenylcyclohexanecarboxylate (II), which was hydrolyzed to afford 4-phenylpimelic acid (III). 5,9-Methanobenzocycloocten-8,10-dione (IV) obtained by cyclization of III with PPA was reduced to 10-hydroxy-5,9-methanobenzocycloocten-8-one (V), which in turn was derived to 8-acetoxy-5,9-methanobenzocyclooctene (VI) by catalytic reduction over Adams catalyst in acetic acid containing a small amount of perchloric acid. VI was hydrolyzed, followed by a Jones oxidation to give 5,9-methanobenzocycloocten-8-one (VII). The oxime (VIII) of VII was submitted to a Beckmann rearrangement with PPA to afford a mixture of 2,3,6,7-tetrahydro-2,7-methano-1H-3-benzazonin-4 (5H)-one (IX-A) and 2,3,6,7-tetrahydro-1,6-methano-1H-4-benzazonin-5 (4H)-one (IX-B) (ratio : ca. 10 : 1), which were separated by fractional recrystallization. Both IX-A and IX-B were reduced with lithium aluminum hydride, followed by Clarke-Eschweiler methylation to give X-A and X-B, respectively. 4-Benzylcyclohexanone (XIV) obtained by catalytic reduction of p-benzylphenol (XIII) and the subsequent oxidation with chromic acid was derived to 3-benzyladipic acid (XV) by nitric acid oxidation, which was then cyclized to 4-oxo-1,2,3,4-tetrahydronaphthalene-2-propionic acid (XVI). The ethyl ester (XVII) of XVI was derived to the oxime (XVIII), which was reduced to an amino-ester followed by cyclization to give 4,5,6,7-tetrahydro-1,6-methano-1H-2-benzazonin-3 (2H)-one (XIX). Reduction of XIX with lithium aluminum hydride and the subsequent methylation afforded XX.

• 社団法人日本薬学会の論文
• 1972-02-25

著者

• 亀谷 哲治

  Institute Of Medicinal Chemistry Hoshi University

• 亀谷 哲治

  Toyama Technical College

• 三橋 監物

  Faculty of Pharmaceutical Sciences, University of Toyama

• 塩谷 俊作

  Toyama Technical College

• 三橋 監物

  Faculty Of Pharmaceutical Sciences Josai University

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