Dual channels for nucleophilic displacements on benzoyl chlorides: Tetrahedral and trigonal-bipyramidal transition states.
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概要
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Nucleophilic substitutions on carbonyl carbons initiated by Cl<SUP>−</SUP>, Ph–CO–Cl+Cl<SUP>−</SUP>→Cl<SUP>−</SUP>+Ph–CO–Cl, were studied with ab initio MO calculations. Two transition states (TS's) were found. One is the "tetrahed-ral" TS caused by the π attack of the nucleophile. The other is the "trigonal-bipyramidal" TS initiated by the σ attack. The coexistence of two TS's is in accord with the proposals of Bentley and Cevasko et al. based on kinetic analyses. Two independent reaction paths are interpreted in terms of the frontier-orbital theory.
- 公益社団法人 日本化学会の論文
著者
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Yamabe Shinichi
Department Of Chemistry Nara University Of Education
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Inagaki Satoshi
Department Of Chemistry Faculty Of Engineering Gifu University
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Minato Tsutomu
Institute for Natural Science, Nara University
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Koyama Tetsuji
Department of Chemistry, Nara University of Education
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