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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 (CC BY 3.0).

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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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