The Reactivity and Electronic Structure of Benzophenothiazones and Benzophenoxazones

研究了5h -苯并[a]吩噻嗪-5- 1及其环取代衍生物在N，N-二甲基甲酰胺（DMF）中滴汞电极上的极谱行为。每个化合物洞都有两个还原波，其半波势与Hammett取代基常数<sigma_p>线性相关。对于母体化合物5h -苯并[a]吩噻嗪-5- 1，在混合溶剂dmf -甲基纤维素溶液中得到的结果与蒽醌的行为相似，可以通过假设母体化合物与其dianion之间发生歧化反应来解释。醌亚胺的碘化反应在丙酮中进行。将3h -吩噻嗪-3- 1或5h -苯并[a]吩噻嗪-5- 1与1,3-碘- 5,5 -二甲基海因在温和条件下反应制备了4-碘- 3h -吩噻嗪-3- 1和6-碘- 5h -吩噻嗪-5- 1。以取代的1,4-萘醌与2-氨基苯硫醇在吡啶中缩合，制备了几种取代的6-苯胺- 5h -苯并[a]苯噻嗪-5- 1衍生物。还研究了所得化合物的还原和乙酰化反应。以5-取代- 2,3-二氯-1,4-萘醌与2-氨基噻吩苯酚缩合为原料，制备了1-取代- 5h -苯并[2,3-a]吩噻嗪-5- 1,1、4-取代- 5h -苯并-[6,5-a]吩噻嗪-5- 1和6-取代-苯并[a][1,4]苯并噻嗪[3,2-c]吩噻嗪衍生物。通过2-氨基-3-羟基吡啶与5-取代- 2,3 -二氯代-1,4-萘醌和6,7-二溴-5,8-喹啉醌的缩合反应，分别制备了1,6-二取代-11-氮杂- 5h -苯并[a]苯恶嗪-5-酮衍生物。得到的化合物经过还原、乙酰化、脱卤和与苯胺反应。用邻氨基苯酚与5-取代- 2,3 -二氯-1,4-萘醌缩合制备了1-和4-取代- 5h -苯并[a]-苯恶嗪-5-酮。

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.