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Molecules 2003, 8(4), 392-400; doi:10.3390/80400392
Article

Kinetic Support for the Generation of a Phenylsulfenium Ion Intermediate

* ,  and
Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
* Author to whom correspondence should be addressed.
Received: 23 January 2003 / Revised: 25 March 2003 / Accepted: 27 March 2003 / Published: 30 April 2003
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Abstract

In the reaction of N-methylbenzenesulfenamide (1) with thioanisole (4) in the presence of trifluoroacetic acid (TFA), the initial rate υ0 of total appearance of 2- and 4-(methylthio)phenyl phenyl sulfides (5) is first and zero order with respect to the initial concentrations of 1 and 4, respectively: υ0=kobs[1]0. The pseudo-first order rate constant kobs is evaluated as 5.2×10-4 sec-1 with varying concentrations of 4 (0.72 to 5.0 M) in a mixture of 4 and CH2Cl2 in the presence of TFA at 10 °C. This data supports the notion that a phenylsulfenium ion intermediate 3 interacting with both the counter ion and the unshared electron-pair of amine is generated by heterolytic N-S scission of the protonated sulfenamide 2, leading to the observed formation of 5.
Keywords: Phenylsulfenium ion intermediate; Kinetic study; Phenylthiolation; Sulfenamide; Thioanisole Phenylsulfenium ion intermediate; Kinetic study; Phenylthiolation; Sulfenamide; Thioanisole
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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MDPI and ACS Style

Takeuchi, H.; Tateiwa, J.-I.; Moriguchi, S. Kinetic Support for the Generation of a Phenylsulfenium Ion Intermediate. Molecules 2003, 8, 392-400.

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