The Rates of Diazomethane Formation from Methylnitrosoamides. The stability of diazomethane solutions towards aqueous alkalis
作者:Michael Pearce
DOI:10.1002/hlca.19800630416
日期:1980.6.6
The rate of hydrolysis of N-methyl-N-nitrosoamides by aqueous alkalis varies greatly. Methylnitrosourea (1) is hydrolyzed rapidly by aqueous KOH-solutions at low temperatures to give a high yield of diazomethane. Under similar conditions, N,N′-dimethyl-N,N′-dinitroso-oxamide (3) is hydrolyzed more slowly, but also gives a good yield of diazomethane. N,N′-Dimethyl-N,N′-dinitrosoterephthal-amide (4)
N-甲基-N-亚硝基酰胺被碱金属水溶液水解的速率变化很大。甲基亚硝基脲(1)在低温下被KOH水溶液迅速水解,得到高产率的重氮甲烷。在相似的条件下,N,N'-二甲基-N,N'-二亚硝基-乙酰胺(3)的水解更缓慢,但重氮甲烷的收率也很高。N,N'-二甲基-N,N'-二亚硝基对苯二甲酰胺(4)和(N-甲基-N-亚硝基)-4-氨基-4-甲基-2-戊酮(5)不易被水溶液水解KOH解决方案。ñ-甲基-N-亚硝基-对甲苯磺酰胺(2)在所测试的化合物中反应性最低。重氮甲烷在甲苯中与含水碱的水解遵循一级动力学。水解速度受碱的浓度和强度以及温度的影响很大。