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首页> 外文期刊>Chemistry: A European journal >Substituent-Dependent Reactivity in the hotodimerization of N-Substituted Dibenz[b,f]azepines
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Substituent-Dependent Reactivity in the hotodimerization of N-Substituted Dibenz[b,f]azepines

机译：N取代的Dibenz [b，f] Azepines热二聚反应中依赖于取代基的反应性

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摘要

The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes)were studied by absorption and emission spectroscopy,by laser flash photolysis,and by preparative irradiation with NMR analysis.In solutions,2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone-or benzophenone-sensitized energy transfer.T-T absorption spectra were measured and absorption coefficients were detemined.The triplet energy tranfer is equally efficiet for N-alkyl dibenzazepines,which do not dimerize.Excited states of npi character in the latter cases are discussed to rationalize the different reactivities.In spite of negligible intersystem crossing of 21 dibenzazepine derivatives,photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm~(-3))as well as in the solid state.A selective anti-configuration of the photodimers was found throughout.
机译：通过吸收和发射光谱，激光闪光光解和NMR制备辐射研究了一系列N-取代的二苯并[b，f]氮杂（亚氨基苯甲酸酯）的光过程。在溶液中，N-的2pi + 2pi光二聚体氰基和N-酰基二苯并ze庚因在丙酮或二苯甲酮敏化的能量转移下通过三重态形成，测量TT吸收光谱并确定吸收系数。三重态能量转移对N-烷基二苯并ze庚因同样有效讨论了后一种情况的npi激发态，以合理化不同的反应性。尽管21种二苯并ze庚因衍生物的体系间交叉可忽略不计，但在浓溶液中直接激发后会形成N-酰基和N-氰基二苯并ze庚因的光二聚体（0.01- 0.1 mol dm〜（-3））以及在固态下都可以发现。

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