Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Photochemical Reactions of Saccharin-$\alpha$-Silylamine Systems. Desilylmethylation of $\alpha$-Silylamine via Single Electron Transfer Pathway

  • Ung Chan Yoon (Department of Chemistry, Pusan National University) ;
  • Young Sim Koh (Department of Chemistry, Pusan National University) ;
  • Hyun Jin Kim (Department of Chemistry, Pusan National University) ;
  • Dong Yoon Jung (Department of Chemistry, Pusan National University) ;
  • Dong Uk Kim (Department of Chemistry, Pusan National University) ;
  • Sung Ju Cho (Department of Chemistry, Pusan National University) ;
  • Sang Jin Lee (Department of Chemistry, Pusan National University)
  • Published : 1994.09.20
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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 with free saccharin and N-trimethylsilylmethyl-N,N-diethyl amine insolution. Photoreaction of N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin in $CH_3OH\;or\;CH_3CN$ results in the generation of desilylmethylated product, N,N-diethyl ammonium saccharin mainly along with benzamide. Photoreaction of N-methylsaccharin with N-trimethylsilylmethyl-N,N-diethyl amine in $CH_3OH$ leads to the production of o-(N-methylcarbamoyl)-N-ethylbenzenesulfonamid e 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 that triplets of saccharin and N-methylsaccharin are the reactive excited states. Based on the consideration of the redox potentials of saccharin and N-trimethylsilylmethyl-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 ${\alpha}$-silylamine.

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  1. Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins vol.31, pp.9, 1994, https://doi.org/10.5012/bkcs.2010.31.9.2453