Photoreduction of benzophenone in benzene. I. Mechanism of secondary reactions
Photoreduction of benzophenone in benzene. I. Mechanism of secondary reactions
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苯中二苯甲酮的光还原。
DOI：
10.1021/j100672a002
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发表时间：
1971
期刊：
影响因子：
--
通讯作者：
J. Dedinas
中科院分区：
文献类型：
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作者：
J. Dedinas
使用脱气溶液和 313 或 366 nm 辐射，在纯度为 99.997% 的区域精制苯中光解二苯甲酮，形成苯频哪醇、联苯和 4-联苯二苯甲醇。二苯甲酮消失的初始量子产率为5.1(+0.8，—1.5)×10-3。苯频哪醇、联苯和4-联苯二苯甲醇的μμ分别为2.5(+0.4，—0.9)X 10~3、1.5(±0.5)X 10~3和1.0(±0.5)X10~4。苯频哪醇显然是由两个羰基结合形成的。苯基自由基由于浓度低，发生苯芳基化反应而不是自由基化合反应。苯基环己二烯基自由基是形成联苯的中间体。它似乎也是形成 4-联苯二苯甲醇的中间体。 300-420 nm 区域的紫外线吸收表明存在一些在氧气气氛中稳定的未鉴定产物。
Benzopinacol, biphenyl, and 4-biphenyldiphenylcarbinol are formed in the photolysis of benzophenone in zone-refined benzene of 99.997% purity using degassed solutions and either 313-or 366-nm radiation. The initial quantum yield of benzophenone disappearance was 5.1 (+ 0.8,—1.5) X 10-3. Benzopinacol, biphenyl, and 4-biphenyldiphenylcarbinol had µµ of 2.5 (+ 0.4,—0.9) X 10~ 3, 1.5 (±0.5) X 10~ 3, and 1.0 (±0.5) X10~ 4, respectively. Benzopinacol is apparently formed by the combination of two ketyl radicals. Phenyl radicals, because of low concentration, underwent benzene arylation rather than radical combination reactions. Phenylcyclohexadienyl radical is an intermediate in the formation of biphenyl. It appears also to be an inter-mediate in the formation of 4-biphenyldiphenylcarbinol. The presence of some unidentified products that are stable in oxygen atmosphere is indicated by the uv absorption in the 300-420-nm region.