Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Mechanistic Studies on the Anormalous Photocycloaddition Reaction of 5-Styryl-1,3-dimethyluracil and 2,3-Dimethyl-2-butene: Formation of the “Apparent Forbidden” [$_\pi4_s + _\pi2_s$] Cycloadduct

  • Eun Ju Shin (Department of Chemistry, Sunchon National University) ;
  • Ho Kwon Kang (Department of Agricultural Chemistry, Sunchon National University) ;
  • Sang Chul Shim (Department of Chemistry, Korea Advanced Institute of Science and Technology)
  • Published : 1991.08.20
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Abstract

Irradiation of 5-styryl-1,3-dimethyluracil (5-SDU) with 2,3-dimethyl-2-butene (DMB) gives a [4+2] cycloadduct which is converted into a [2+2] cycloadduct on the prolonged irradiation. Triplet sensitization, quenching, and external heavy atom effect on the [4+2] photocycloaddition reaction demonstrate the singlet pathway and salt effect excludes a radical ion pair precursor possibility. Polar solvents increase the reaction efficiency implying a polar exciplex involvement in the [4+2] photocycloaddition reaction. Inverse temperature dependence both on the reaction and DMB fluorescence quenching of 5-SDU indicates the presence of a singlet exciplex intermediate.

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