摘要
N-哌啶乙酰胺负离子和一系列溴代芳烃在液氨中的光反应导致酰胺α-碳原子的芳基化,但在溴苯中,光产物组成很复杂:35%1,2-二苯乙烷;2%联苯;5%苯和1.5%N-哌啶苯乙酰胺.MO计算结果显示N-哌啶苯乙酰胺阴离子游离基的奇电子主要配置在哌啶基部分.β-裂解和苄基游离基二聚形成的1,2-二苯乙烷成为主要产物(ArNu)奇电子优先分布在稠环部分的奇电子转移给基态的ArX,从而生成亲核取代产物.
The photostimu lated reaction of N-piperidinyl acetamide anion with a series of chloroarenes in liquid ammonia led to the arylation at α-carbon of the amide. However, a mass photoproduct distribution consisting of 1.2-diphenylethanne (35%). biphenyl (2%), benzene (5%) and N-piperdinyl benzoacetamide was observable. In the case of chlorobenzene MO calculation indicated that the odd electron of (PhCH2COPi)- might be heavily populated in the piperdinyl portion of the redical anion. Predominant β-scission of (PHCH2COPi)-follwed by dimerization of benzyl radical gave 1,2-diphenylethane as the major product.Residence of the odd electron of (ArNu)-at the polycylic aryl moiety resulted in the electron to transfer ground ArX and formation of the nucleophilic substitution product.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1994年第5期421-426,共6页
Acta Chimica Sinica
基金
国家自然科学基金资助的项目
