Kinetic study on the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines.

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概要

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• Kinetics for the alkaline hydrolysis of <I>S</I>,<I>S</I>-diaryl-<I>N</I>-bromosulfilimines were carried out in aqueous methanol. The observed pseudo-first-order rate constants were found to give a linear correlation with the concentration of sodium hydroxide, <I>k</I>=<I>k</I><SUB>1</SUB>+<I>k</I><SUB>2</SUB>[NaOH]. The first-order rate constants <I>k</I><SUB>1</SUB> showed a large negative Hammett ρ value (−2.43) for the substituent effect on the phenyl group, nearly zero activation entropy (−0.9±13.1 JK<SUP>−1</SUP>mol<SUP>−1</SUP>) and a relatively large <I>m</I> value (0.638) against the solvent ionizing power <I>Y</I> value suggesting that the reaction process for <I>k</I><SUB>1</SUB> close to S<SUB>N</SUB>l. The salt effect, the deuterium solvent isotope effect and the steric effect are also in accord with the S<SUB>N</SUB>l mechanism. On the other hand, the second-order rate constants <I>k</I><SUB>2</SUB> revealed a small Hammett ρ value, a negative activation entropy (−44.0±4.0 JK<SUP>−1</SUP>mol<SUP>−1</SUP>), a small <I>m</I> value (0.153) and a steric deceleration by ortho substituents showing that the reaction for <I>k</I><SUB>2</SUB> is S<SUB>N</SUB>2-like. The salt effect and the solvent isotope effect are also compatible with the S<SUB>N</SUB>2-like mechanism. Meanwhile, the <I>k</I><SUB>1</SUB> for <I>S</I>,<I>S</I>-diphenyl-<I>N</I>-halosulfilimines remarkably increased in the order of <I>N</I>-iodo<<I>N</I>-bromo<<I>N</I>-chloro. This reactivity might be due to the lone pair-lone pair repulsion at the reactant state. From these observations, the alkaline hydrolysis of <I>S</I>,<I>S</I>-diaryl-<I>N</I>-halosulfilimines was confirmed to proceed via concurrent two mechanisms, the S<SUB>N</SUB>2′-like mechanism involving nitridosulfonium cation (><SUP>+</SUP>S≡N) as an intermediate and the S<SUB>N</SUB>2′-like mechanism with the transition state in which the N-X bond cleavage is more progressed than the S–O bond formation with nucleophiles (<SUP>−</SUP>OH, <SUP>−</SUP>OMe).

• 公益社団法人 日本化学会の論文

著者

• Shimasaki Choichiro

  Department Of Chemical And Biochemical Engineering Faculty Of Engineering Toyama University

• Kita Hiroshi

  Department Of Biochemical Engineering And Science Kyushu Institute Of Technology

• Tsukurimichi Eiichi

  Department Of Chemical And Biochemical Engineering Faculty Of Engineering Toyama University

• Fujii Hiroshi

  Department Of Biochemistry Niigata University School Of Medicine

• Yoshimura Toshiaki

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

• Shimasaki Choichiro

  Department of Industrial Chemistry, Faculty of Engineering, Toyama University

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