Aromatic Sulfonylation. I. Kinetics and Kinetic Isotope Effects in the Sulfonylation
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概要
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<I>p</I>-Toluenesulfonylation of toluene, chlorobenzene and bromobenzene in the presence of aluminum chloride was investigated in methylene chloride at 0–20°C. The rate was equal to <I>k</I><SUB>3</SUB>[TsCl][AlCl<SUB>3</SUB>][ArH]. Kinetic hydrogen isotope effects were found for <I>p</I>-deuteriotoluene (<I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB>=2.8) and <I>p</I>-deuteriochlorobenzene (<I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB>=1.98). Infrared studies indicated that not a sulfonyl cation but TsCl-AlCl<SUB>3</SUB> complex was present in the medium. Substitution took place exclusively at <I>para</I> positions for halobenzenes, but 13.4% ortho and 86.6% <I>para</I> isomers were obtained for toluene. Partial rate factors for <I>para</I> positions were 52.5(PhCH<SUB>3</SUB>), 0.224(PhCl) and 0.164(PhBr). A plausible reaction mechanism was proposed, in which the abstraction of proton from the σ-complex was rate-determining.
- 公益社団法人 日本化学会の論文
著者
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Minato Hiroshi
Department Of Electrical Engineering And Computer Science Tufts University
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KOBAYASHI Michio
Department of Chemistry and Biological Science, College of Science and Engineering, Aoyama Gakuin Un
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Kohara Yoshio
Department of Chemistry, Faculty of Science, Tokyo Metropolitan University
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Kohara Yoshio
Department of Chemistry, Tokyo Metropolitan University
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