A Kinetic Study of Alkaline Hydrolysis of β-Arylaminoacrolein

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概要

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• Alkaline hydrolysis of β-arylaminoacrolein (1), a vinylog of amides, was studied kinetically. The kinetics involved terms both first and second order in hydroxide ion. The first step of the reaction (rate constant k_1) is an attack of hydroxide ion on the β-position of 1,and the tetrahedral intermediate formed was partitioned in two ways : one without the aid of hydroxide ion (k_2(k_1/k_<-1>)), and the other with the aid of hydroxide ion (k_3(k_1/k_<-1>)). The rate constants, k_1,k_2(k_1/k_<-1>) and k_3(k_1/k_<-1>) were obtained for 12 substrates, and the activation parameters, ΔH^≠ and ΔS^≠, of each step were evaluated for 5 substrates. The k_2/k_<-1> values decreased with increasing electron-withdrawing effect of aryl substituents. The differences of ΔH_f between the intermediates and the starting materials were evaluated by molecular orbital (MO) calculatins. The results showed that k_2 decreases with increasing electron-withdrawing effect of the substitutents. The second step of the second-order reaction, k_2(k_1/k_<-1>), is partitioning of anionic intermediates catalyzed by water as a general acid. While the second step of the third-order reaction, k_3(k_1/k_<-1>), for "typical" substrates is departure of the arylamino group from the anionic intermediates catalyzed by both hydroxide ion and water, that for β-(p-nitrophenylamino)acrolein (1j) is direct expulsion of p-nitroanilide ion from the dinegatively charged intermediate.

• 社団法人日本薬学会の論文
• 1989-11-25

著者

• 尾能 満智子

  東邦大薬

• 尾能 満智子

  School Of Pharmaceutical Sciences Toho University

• 等々力 玲子

  School of Pharmaceutical Sciences, Toho University

• 湯川 美穂

  福岡大学薬学部

• 後藤 良宣

  福岡大学薬学部

• 後藤 良宣

  Faculty of Pharmaceutical Sciences, Fukuoka University

• 田村 眞造

  School of Pharmaceutical Sciences, Toho University

• 三嶽 秋久

  School of Pharmaceutical Sciences, Toho University

• 湯川 美穂

  Faculty of Pharmaceutical Sciences, Fukuoka University

• 田村 眞造

  School Of Pharmaceutical Sciences Toho University

• 田村 真造

  東邦大学 薬

• 等々力 玲子

  School Of Pharmaceutical Sciences Toho University

• 後藤 良宣

  Faculty Of Pharmaceutical Sciences Fukuoka University

• Todoriki R

  Toho Univ. Chiba Jpn

• 三嶽 秋久

  School Of Pharmaceutical Sciences Toho University

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