Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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New Mechanism for the Reaction of Thianthrene Cation Radical Perchlorate with tert-Butyl Peroxide

  • Park, Bo-Kyung (Department of Chemistry Education, Chonnam National University) ;
  • Sohn, Chang-Kook (Department of Chemistry Education, Chonnam National University) ;
  • Lee, Wang-Keun (Department of Chemistry Education, Chonnam National University)
  • Published : 2002.01.20
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Abstract

A new reaction mechanism is proposed for the reaction of thianthrene cation radical perchlorate $(Th^{+{\cdot}}CIO_4^-}$ and tert-butyl peroxide in acetonitrile at room temperature on the basis of experimental and theoretical results. Rapid C-O bond rupture instead of O-O bond cleavage was observed by a good peroxy radical trapping agent, thianthrene cation radical. Products were N-tert-butyl acetamide, thianthrene 5-oxide (ThO), thianthrene 5,5-dioxide $(SSO_2)$, and thianthrene (Th). Thianthrene 5,10-dioxide (SOSO) was not obtained. A comparative computational study of the cation radical of tert-butyl peroxide is made by using B3LYP and CBS-4. The computational results are helpful to explain the reaction mechanism.

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References

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