Photochemical Reactions of Saccharin-α-Silylamine Systems. Desilylmethylation of α-Silylamine via Single Electron Transfer Pathway

다국어 초록 (Multilingual Abstract)

Photochemical reactions of saccharin with tertiary amines were explored. Saccharin was found to undergo an acid-base reaction with N-trimethylsilylmethyl-N, N-diethyl amine to form N-trimethylsilylmethyl-N, N-diethyl ammonium saccharin salt which is in equilibrium wit free saccharin and N-trimethylsilymethyl-N, N-diethyl amine in solution. Photoreaction of N-trimethylsilymethy-N, N-diethyl ammonium sacchrin in CH₃OH or CH₃CN result in the generation of desilylmethylated product N, N-diethyl ammonium sacchrin mainly along with benzamide. Photoreaction of N-methylsaccharin with N-trimethylsilymethyl-N, N-diethyl amine in CH₃OH leads to the production of o-(N-methykcarbamoyl)-N-ethylbenzenesulfonamide as the major product along with N-methylbenzamide as the minor product. On the other hand, photoreaction of N, N, N-triethyl ammonium saccharin, generated from saccharin and triethylamine, produces N-methylbenzamide as the exclusive product. These photoreactions are quenched by oxygen indicating redox potentials of saccharin and N-trimethylsilymethyl-N, N-diethyl amine, and the nature of photoproducts, pathways involving initial triplet state single electron transfer are proposed for photoreactions of the saccharins with the α-silyamine.