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The Rates of Diazomethane Formation from Methylnitrosoamides. The stability of diazomethane solutions towards aqueous alkalis
Author(s) -
Pearce Michael
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630416
Subject(s) - diazomethane , chemistry , hydrolysis , aqueous solution , yield (engineering) , toluene , organic chemistry , nuclear chemistry , metallurgy , materials science
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.