Synthesis of Dibenzo [b, f] cycloprop [d] azepine Derivatives. II. Introduction of a Cyclopropane Ring by the Dichloromethylene Transfer Reaction
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概要
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An improved method for the synthesis of 1,1a, 6,10b-tetrahydrodibenzo [b, f] cycloprop-[d] azepine (3) was described. Thus, 5H-dibenz [b, f] azepine (1) was formylated and dichloro-cyclopropanated with dichloromethylene generated from chloroform and aqueous sodium hydroxide in the presence of a phase-transfer catalyst to yield 1,1-dichloro-1a, 10b-dihydrodibenzo [b, f] cycloprop [d] azepine-6 (1H)-carbaldehyde (2). The latter compound and its deformylated product, 1,1-dichloro-1,1a, 6,10b-tetrahydrodibenzo [b, f] cycloprop [d] azepine (5), were reduced to 3 with sodium in liquid ammonia. 5-Acetyl-, 5-carbamoyl, 5-methyl- and 5-(3-chloropropyl)-5H-dibenz [b, f] azepines (6,8,11 and 14), when treated with the dichloromethylene, gave the corresponding dichloro-cyclopropanation products and some other products, in which the substituents had reacted simultaneously with dichloromethylene in several fashions. The reduction of 5 under drastic conditions yielded 5,6,7,12-tetrahydrodibenz [b, g]-azocine (20) and 10H-indolo [1,2-a] indole (21). cis-and trans-1-Chloro-1,1a, 6,10b-tetra-hydrodibenzo [b, f] cycloprop [d] azepines (23,R=H and 24,R=H), on the other hand, were the main products of catalytic hydrogenation of 5. Conformational aspects of the N-methyl derivatives 23 (R=CH_3) and 24 (R=CH_3) were discussed.
- 社団法人日本薬学会の論文
- 1978-03-25
著者
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川野 泰彦
Central Research Division, Takeda Chemical Industries, Ltd.
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川野 泰彦
Central Research Division Takeda Chemical Industries Ltd.
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川島 健也
Central Research Division, Takeda Chemical Industries, Ltd.
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更家 崇弘
Central Research Division, Takeda Chemical Industries, Ltd.
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石黒 敏弘
Central Research Division, Takeda Chemical Industries, Ltd.
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川島 健也
Central Research Division Takeda Chemical Industries Ltd.
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石黒 敏弘
Central Research Division Takeda Chemical Industries Ltd.
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更家 崇弘
Central Research Division Takeda Chemical Industries Ltd.
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