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The Reactivity and Electronic Structure of Benzophenothiazones and Benzophenoxazones

苯并吩噻腙和苯并吩恶腙的反应活性和电子结构

基本信息

批准号：
60470086
负责人：
UENO Yoshio
金额：
$ 4.67万
依托单位：
Nagoya Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

项目摘要

The polarographic behavior of 5H-benzo[a]phenothiazin-5-ones and its ring-substituted derivatives at a dropping mercury electrode was studied in N,N-dimethylformamide(DMF). Each compound cave well-defined two reduction waves, the half-wave potentials of which lineary corrlated with the Hammett substituent constant <sigma_p> . For the parent compound, 5H-benzo[a]phenothiazin-5-one, the similarity with the behavior of anthraquinone, the results obtained in a mixed solvent, DMF-methylcellosolve, were explained by assuming a disproportionation reaction between the parent compound and its dianion.The iodination of quinone imines were performed in acetone. 4-Iodo-3H-phenothiazin-3-one and 6-Iodo-5H-benzo[a]phenothiazin-5-one were prepared by reacting 3H-phenothiazin-3-one or 5H-benzo[a]phenothiazin-5-one with 1,3-Iodo-5, 5-dimethylhydantoin under mild condition. Several substituted 6-anilino-5H-benzo[a]phenothazin-5-one derivatives were prepared by condensation of substituted 1,4-naphthoquinones with 2-aminobenzenethiol in pyridine. The reduction and acetylation of the resulting compounds were also investigated. The 1-substituted-5H-benzo[2,3-a]phenothiazin-5-one, 4-substituted-5H-benzo-[6,5-a]phenothiazin-5-one and 6-substituted-benzo[a][1,4]benzothiazino[3,2-c]-phenothiazine derivatives were prepared by the condensation of 5-substituted-2, 3-dichloro-1,4-naphthoquinones with 2-aminothiophenol.The 1,6-disubstituted- and 4,6-disubstituted-11-aza-5H-benzo[a]phenoxazin-5-one as well as 6-substituted-11-aza-5H-pyrido[a]phenoxazin-5-one derivatives were preparedby condensation of 2-amino-3-hydroxy-pyridine with 5-substituted-2, 3-dichalogeno-1,4-naphthoquinones and 6,7-dibromo-5,8-quinolinequinone respectively. The resulting compounds were subjected to reduction, acetylation, dehalogenation and reaction with aniline. The 1- and 4-substituted-5H-benzo[a]-phenoxazin-5-ones were prepared by the condensation of o-aminophenol with 5-substituted-2, 3-dichloro-1,4-naphthoquinones.

本文研究了5 H-苯并[a]吩噻嗪-5-酮及其环上取代衍生物在N，N-二甲基甲酰胺（DMF）介质中的滴汞电极上的极谱行为。每个化合物都有两个明确的还原波，其半波电位与Hammett取代基常数线性相关<sigma_p>。对于母体化合物5 H-苯并[a]吩噻嗪-5-酮，在DMF-甲基溶纤剂混合溶剂中得到的结果与蒽醌的行为相似，通过假定母体化合物与其二价阴离子之间的反离子化反应来解释。以3 H-吩噻嗪-3-酮或5 H-苯并[a]吩噻嗪-5-酮与1，3-碘-5，5-二甲基乙内酰脲在温和条件下反应，合成了4-碘-3H-吩噻嗪-3-酮和6-碘-5H-苯并[a]吩噻嗪-5-酮。通过取代1，4-萘醌与2-氨基苯乙胺在吡啶中缩合，合成了几种取代6-苯胺基-5H-苯并[a]吩噻嗪-5-酮衍生物。对所得化合物的还原和乙酰化反应也进行了研究。5-取代-2，3-二氯-1，4-萘醌与2-氨基苯硫酚缩合，合成了1-取代-5H-苯并[2，3-a]吩噻嗪-5-酮、4-取代-5H-苯并[6，5-a]吩噻嗪-5-酮和6-取代-苯并[a][1，4]苯并噻嗪并[3，2-c]吩噻嗪衍生物。通过2-氨基-3-羟基吡啶分别与5-取代-2，3-二卤代-1，4-萘醌和6，7-二溴-5，8-喹啉酮缩合，合成了6-二取代-11-氮杂-5H-苯并[a]吩恶嗪-5-酮和6-取代-11-氮杂-5H-吡啶并[a]吩恶嗪-5-酮衍生物。所得化合物经还原、乙酰化、脱卤及与苯胺反应制得。以邻氨基苯酚和5-取代-2，3-二氯-1，4-萘醌为原料合成了1-和4-取代-5H-苯并[a]-吩恶嗪-5-酮。