Electrophilic aromatic substitution. 14. [1] A kinetic, NMR, and Raman study of the aluminum chloride-catalyzed reaction of p-toluene-sulfonyl chloride with benzene and toluene in dichloromethane
✍ Scribed by Franklin P. DeHaan; Paul Y. Ahn; Carl R. Kemnitz; Steven K. Ma; Jim Na; Bimal R. Patel; Richard M. Ruiz; Randy M. Villahermosa
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 135 KB
- Volume
- 30
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Vacuum line kinetic studies of the reaction of p-toluenesulfonyl chloride and benzene or toluene, using aluminum chloride as the catalyst and dichloromethane as the solvent were determined at 25ЊC by means of gas chromatography. The reaction is first-order in arene, tosyl chloride, and in AlCl 3 as catalyst. Noncompetitive results are with a prod-k /k ϭ 22 Ϯ 7 T B uct sulfone isomer distribution: ortho, meta, and para With hex-14 Ϯ 1%; 4.3 Ϯ 0.2%; 82 Ϯ 1%. adeuteriobenzene was determined to be Rate constant ratios and product k /k 1.8 Ϯ 0.1. H D isomer distributions were also determined competitively: with AlCl 3 , % ortho, k /k ϭ 30 Ϯ 2; T B % meta, %para, with SbCl 5 , % ortho % meta, 13 Ϯ 1; 4.0 Ϯ 0.5; 84 Ϯ 3; k /k ϭ 40 Ϯ 4; 10.3 Ϯ 0.4; T B
and % para, The ratio for AlCl 3 and the meta sulfone product per-4.7 Ϯ 0.2; 85.0 Ϯ 0.5. k /k T B centages for both AlCl 3 and SbCl 5 are considerably higher than those reported in the literature. NMR and Raman studies suggest a molecular complex between p-tosyl chloride and AlCl 3 , with coordination through oxygen as the dominant species and the probable electrophile in CH 2 Cl 2 . A reaction mechanism consistent with the kinetic and spectroscopic results is proposed.