光カルボキシル化　Ｉ　　スチレン‐アミン系の光化学反応　　ラジカルアニオンを用いる二酸化炭素の固定

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  • Photochemical Reaction of Styrenes with Triethylamine -Photofixation of Carbon Dioxide by Radical Aniont-
  • スチレン アミンケイ ノ コウカガク ハンノウ ラジカル アニオン オ モチイ

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Photochemical reaction of styrene and a-methylstyrene with triethylamine gave 1: 1 adduct [2] and reduced products [3] and C 4D as main products. In hexane, [2]was obtained preferably while [3] and [4] were favored in acetonitrile. An addition of methanol did not affect the product formation in acetonitrile, but depressed the formation of [2] and enhanced the formation of [3 ] and [4] in hexane. The analysis of the products formed in the presence of methanol-d suggests that the styrene-triethylamine exciplex reacts with methanol at the p-position of styrene which is supposed to be nagatively charged. Furthermore, the styrene radical anion is effectively formed in acetonitrile. Scheme 1 is proposed as the reaction mechanism. Carbon dioxide did not react with the exciplex, but reacted with the radical anion effectively to afford carboxylic acids [5 ]-[8] (total quantum yield ca. O.3). Similar reactions with other styrene derivatives, i. e., β-methylstyrene, indene, and 1, 1-diphenylethylene, gave the corresponding carboxylic acids in total yields of 42, 69, and 43%, respectively. In the case of stilbene, methyl cinnamate, and cinnamonitrile, however, the acids were not detected and the reduction products were obtained, suggesting the formation of radical anion. Localization of a negative charge at the β-olefinic carbon atom seems to be essential for the formation of the carboxylic acids. t Photochemical Carboxylation. I.

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