Laser Flash Photolysis and CIDNP Studies of 1-Naphthyl Acetate Photo-Fries Rearrangement
Laser Flash Photolysis and CIDNP Studies of 1-Naphthyl Acetate Photo-Fries Rearrangement
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1-乙酸萘酯光弗赖斯重排的激光闪光光解和 CIDNP 研究
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
R. Sagdeev
中科院分区：
文献类型：
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作者：
N. Gritsan;Y. Tsentalovich;A. Yurkovskaya;R. Sagdeev
使用稳态和时间分辨 CIDNP 和闪光光解方法详细研究了 1-萘基乙酸酯 (I) 在乙腈和甲醇中的光弗赖斯重排。主要反应通道是 I 通过激发单线态衰变，室温下乙腈中的量子产率为 0.17 ± 0.02，甲醇中的量子产率为 0.42 ± 0.04。检测了萘氧基自由基和乙酸1-萘酯三重态的吸收光谱。在乙腈和甲醇中三线态的量子产率估计分别为 0.4 ± 0.2 和 0.35 ± 0.17。已经确定，三重态自由基对对照片-弗赖斯重排产物的 CIDNP 做出了主要贡献。假设参与了 I 的两个不同三重态的过程。最低三重态的主要衰变通道是三重态-三重态湮灭，而光-弗里斯重排产物的CIDNP是由具有生命周期的I的上三重态衰变产生的。
The steady-state and time-resolved CIDNP and flash photolysis methods were used in a detailed study of the photo-Fries rearrangement of 1-naphthyl acetate (I) in acetonitrile and methanol. The main reaction channel is the decay of I through the excited singlet state with the quantum yields 0.17 ± 0.02 in acetonitrile and 0.42 ± 0.04 in methanol at room temperature. The absorption spectra of the naphthoxyl radical and triplet state of 1-naphthyl acetate were detected. The quantum yield of triplet was estimated as 0.4 ± 0.2 and 0.35 ± 0.17 in acetonitrile and methanol, respectively. It has been established that the triplet-born radical pairs make a main contribution to the CIDNP of the photo-Fries rearrangement products. The involvement in the process of two different triplet states of I was supposed. The main decay channel of the lowest triplet state is the triplet−triplet annihilation, while the CIDNP of photo-Fries rearrangement products results from the decay of the upper triplet state of I with a lifet...