化学学报 ›› 1981, Vol. 39 ›› Issue (3): 215-227. 上一篇    下一篇

论文

Knorr-Paal缩合反应机制的研究Ⅰ.

曾广植, 严家(泩生), 沈定璋   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1979-02-22 发布日期:2013-06-03

A STUDY ON THE MECHANISM OF KNORR-PAAL CONDENSATIONS Ⅰ.

ZENG GUANG-ZHI(TSENG KUANG-CHIH), YAN JIA-SHENG, SHEN DING-ZHANG   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1979-02-22 Published:2013-06-03

从Knorr-Paal缩合反应动力学研究得出:(1)速率-pH图有钟罩形曲线;(2)负活化熵大,活化能低;(3)对-取代苯甲酸催化对-乙氧苯胺与β-二酮缩合的Brönsted α值为0.25;(4)以ρ+=-0.881作Hammett图与速率相关比ρ-ρ好;(5)苯胺类分别与β-二酮或乙酰丙酮缩合,两者有很好线性的自由能关系.可见缩合机制应是简单的羰基加成和消除(脱水)过程.

The following points derived from a kinetic study of the Knorr-Paal condensation prove that its mechanism can be no other than a simple carbonyl addition and eliminative dehydration: (1) It has the most striking feature of a characteristic bell-shaped graph of reaction rate as a function of pH. (2) It has unusually large negative activation entropy as well as extremely low activation enthalpy. (3) For the conden-sation of ρ-qrethogyaniline and β-diketone with ρ-substituted benzoic acids as catalysts, it also has the characteristic Brönsted α value 0.25. (4) It has a Hammett plot of ρ+=-0.881 which also correlates with the rates mnch better than ρ- or ρ. (5) These condensations have excellent LFR with those of acetylacetone with the same group of anilines.