Hydrolysis of Electron-Accepting Esters Catalyzed by Electron--Donating Azoles “Nonclassical” Michaelis Menten Mechanism

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  • TAKEISHI Makoto
    Department of Materials Science and Engineering, Faculty of Engineering,
  • YAHAGI Kazuhiro
    Department of Materials Science and Engineering, Faculty of Engineering,
  • OKUYAMA Kohsaku
    Department of Materials Science and Engineering, Faculty of Engineering,
  • MASUYAMA Yoshiyuki
    Department of Materials Science and Engineering, Faculty of Engineering,
  • SATO Rikiya
    Department of Materials Science and Engineering, Faculty of Engineering,

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Other Title
  • 電子供与性アゾール触媒による電子受容性エステルの加水分解-非古典的Michaelis-Menten機構-
  • デンシ キョウヨセイ アゾール ショクバイ ニ ヨル デンシ ジュヨウセイ エ

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Abstract

The hydrolyses of electron-accepting esters catalyzed by electron-donating azoles were investigated.1, 2, 3-Benzotriazole accelerated the hydrolysis of 1-naphthyl 3, 5-dinitrobenzoate in the pH range of 7 to 11, whereas the hydrolysis above pH 12 was retarded by the azole. The retardation was attributed to the formation of a charge-transfer complex between the ester and the anionic deprotonated 1, 2, 3-benzotriazole the nucleophilic attack by hydroxide ion on the ester is inhibited by the formation of the anionic complex. This inhibition is expected to take place over all the pH region above neutrality; therefore, the acceleration by the azole below pH 11 can be ascribed to bimolecular nucleophilic attack of free 1, 2, 3benzotriazolide anions on the free ester molecules that overrides the inhibition. The kinetics is expressed by a hyperbolic function which is similar to that for the Michaelis-Menten mechanism in enzymic reactions; however, this catalytic reaction is explained by the “nonclassical”Michaelis-Menten mechanism proposed by Menger.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1992 (11), 1356-1362, 1992-11-10

    The Chemical Society of Japan

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