化学学报 ›› 1982, Vol. 40 ›› Issue (8): 720-729. 上一篇    下一篇

论文

Knorr-Paal缩合反应机制的研究Ⅱ

曾广植, 严家(泩生), 沈定璋, 陈镜泓   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1980-03-10 发布日期:2013-06-03
  • 通讯作者: 曾广植

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

ZENG GUANG-ZHI, YAN JIA-SHENG, SHEN DING-ZHANG, CHEN JING-HONG   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1980-03-10 Published:2013-06-03

在Knorr-Paal缩合合成工作中,最好按我们已发现的两种可能反应过程和四种催化情况考虑合成的条件.强亲核性胺的缩合无须用催化剂或可用碱性催化剂;弱亲核胺或具有较大空间位阻的胺的缩合则必须用酸性催化剂.反应速率以催化酸所形成的铵盐与游离胺的比率接近1时达极大值(此时介质的pH接近于胺的pKa).故反应活性很差的胺必需用Lewis酸催化才能引起反应.因本反应中各步均有颇强的可逆性,宜采取措施以打破其不利的化学平衡和避免过多的副反应.本文还讨论了文献中谈到的、在合成上遇到的七种困难情况和绕过这些困难的可能途径.

When Knorr-Paal condensation is to be employed in synthetic work, the experimental conditions must be designed according to the two feasible reaction pathways and four possible catalytic conditions which we have so far discovered in mechanism studies. For the condensation with strongly nudeophilie amine no catalyst or only basic catalyst should be used while for that with weakly nucleophilic amince ox with one of considerable steric resistance an acid catalyst ought to be applied.