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Kinetic Support for the Generation of a Phenylsulfenium Ion Intermediate
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; in revised form: 25 March 2003 / Accepted: 27 March 2003 / Published: 30 April 2003
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=kobs0. 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
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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.
Takeuchi H, Tateiwa J-I, Moriguchi S. Kinetic Support for the Generation of a Phenylsulfenium Ion Intermediate. Molecules. 2003; 8(4):392-400.
Takeuchi, Hiroshi; Tateiwa, Jun-ichi; Moriguchi, Shintaro. 2003. "Kinetic Support for the Generation of a Phenylsulfenium Ion Intermediate." Molecules 8, no. 4: 392-400.