Relationships between Electron Structures of N-Methylolamines and their Reactivity in the mannich reaction

✍ Scribed by Yuejun Zhang; Wei Dong; Jie Shi; Weimin Li

• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 398 KB
• Volume: 19
• Category: Article
• ISSN: 0721-3115
• DOI: 10.1002/prep.19940190208

✦ Synopsis

Abstract

The electron structures of various unstable N‐methylolamines and their imine cations formed during the urotropine nitrolysis process were studied by SCF‐CNDO/2 computation. The relative tendency of forming imine cations from such N‐methylolamine molecules was assessed by the computation values of Mulliken bond order (M~co~) of CO bond and the negative values (−E~co~) of two‐atome energy. The electrophilic order of imine cations described by the products (Z~co~) of carbocation's static charges and the rations of partition functions Q~s~/Q~p~ between s and p electrons, were used to express the relative reactivity of the Mannich reaction intermediates. Experimental results were satisfactorily explained by the calculated values, and the reactivity of nitrolysis fragments was successfully predicted by the defined values.