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The Rates of Diazomethane Formation from Methylnitrosoamides. The stability of diazomethane solutions towards aqueous alkalis

✍ Scribed by Michael Pearce


Publisher
John Wiley and Sons
Year
1980
Tongue
German
Weight
267 KB
Volume
63
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

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), and (N‐methyl‐N‐nitroso)‐4‐amino‐4‐methyl‐2‐pentanone (5) are less easily hydrolyzed by aqueous KOH‐solutions. N‐Methyl‐N‐nitroso‐p‐toluenesulfonamide (2) was the least reactive out of those tested. The hydrolysis of diazomethane in toluene with aqueous bases follows first order kinetics. The hydrolysis rate is greatly influenced by the concentration and strength of the base and temperature.