Solvent Effects on the Photoamination of 1-Amino-2,4-dibromoanthra- quinone. I. Photoamination in Benzene via Intramolecular Charge Transfer Excited Triplet State
Solvent Effects on the Photoamination of 1-Amino-2,4-dibromoanthra- quinone. I. Photoamination in Benzene via Intramolecular Charge Transfer Excited Triplet State
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溶剂对 1-氨基-2,4-二溴蒽醌光胺化的影响。
DOI：
10.1246/bcsj.51.1793
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发表时间：
1978
影响因子：
4
通讯作者：
M. Hida
中科院分区：
文献类型：
--
作者：
H. Inoue;M. Hida
在可见光照射下，1-氨基-2,4-二溴蒽醌(1)的4位溴原子被丁胺和苯胺取代。在乙醇中，溶解氧促进了反应，而三元猝灭剂蒽对反应的影响不大。在苯中，溶解氧延缓了反应，蒽有相当大的猝灭作用。动力学分析表明，在乙醇中，1的光胺化主要通过1在S1（1CT）与基态氧的相互作用进行，而在苯中，光胺化主要通过1的T1（3CT）与基态氧的相互作用进行。讨论了在苯中反应的详细机理，并计算了各反应过程的速率常数，包括上激发T2（3nπ*）能级的失活常数。
The bromine atom at the 4 position of 1-amino-2,4-dibromoanthraquinone (1) was substituted by butylamine and aniline by the irradiation of visible light. In ethanol the dissolved oxygen promoted the reaction and anthracene, a triplet quencher, had little effect. In benzene, the dissolved oxygen retarded the reaction and anthracene had a considerable quenching effect. Kinetic analysis indicated that in ethanol the photoamination of 1 proceeds mainly through the interaction of 1 in S1(1CT) with the ground state oxygen, while in benzene it does through the T1(3CT) of 1 without the aid of oxygen. The detailed reaction mechanism in benzene has been discussed and the rate constant of each process including the deactivation constant of the upper excited T2(3nπ*) level evaluated.