Aromatic Sulfonylation. II. Attacking Species under Various Conditions.
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概要
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<I>p</I>-Toluenesulfonylation of toluene and anisole in the presence of AlCl<SUB>3</SUB>, SbCl<SUB>5</SUB> or TiCl<SUB>4</SUB> was investigated in methylene chloride, nitromethane and nitrobenzene. Substitution took place at 8.6–13.4% and 86.6–91.4% <I>para</I> positions for toluene in methylene chloride, but 42.0–45.7% <I>ortho</I> and 54.2–58.0% <I>para</I> isomers were obtained in nitromethane and nitrobenzene. Sulfonylation of toluene with <I>p</I>-CH<SUB>3</SUB>C<SUB>6</SUB>H<SUB>4</SUB>SO<SUB>2</SUB><SUP>+</SUP> ClO<SUB>4</SUB><SUP>−</SUP> afforded 44.8–46.3% <I>ortho</I> and 53.7–55.2% <I>para</I> isomers. Partial rate factors for toluene were <I>p<SUB>f</SUB></I>=52.5 in methylene chloride, <I>o<SUB>f</SUB></I>=12.6±0.9, <I>p<SUB>f</SUB></I>=31.4±2.0 in nitromethane, and <I>o<SUB>f</SUB></I>=16.0±1.7, <I>p<SUB>f</SUB></I>=38.3±4.2 with <I>p</I>-CH<SUB>3</SUB>C<SUB>4</SUB>H<SUB>4</SUB>SO<SUB>2</SUB><SUP>+</SUP>ClO<SUB>4</SUB><SUP>−</SUP>. A plausible mechanism is proposed, in which the attacking species is TsCl-MCl<I><SUB>n</SUB></I> complex in methylene chloride, but it is an ion pair, ArSO<SUB>2</SUB><SUP>+</SUP>MCl<SUP>−</SUP><SUB><I>n</I>+1</SUB>, in nitromethane and nitrobenzene.
- 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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