Science of Synthesis

Kubik, S., Science of Synthesis, (2010) 41, 513.

Reaction of N-nitrosoamides with bases such as potassium carbonate or potassium hydroxide in alcoholic solvents or potassium tert-butoxide in diethyl ether causes cleavage of the acyl group and formation of the corresponding alkyldiazenolates.[‌69‌] N-Nitrosocarbamates react in a similar manner,[‌70‌–‌72‌] whereas N-nitrosoureas give cyanate and the corresponding alkyldiazenolate (‌Scheme 13‌).[‌73‌–‌75‌] The chemistry of alkyldiazenolates, formed exclusively in the Z configuration by these procedures,[‌76‌] has been studied in detail.[‌68‌] In protic solvents, alkyldiazenolates are rapidly protonated to form alkanediazonium compounds,[‌77‌–‌81‌] which can undergo the usual decomposition and substitution reactions or give diazo compounds upon deprotonation. Thus, this reaction is also a useful strategy for the preparation of diazo compounds {see Science of Synthesis, Vol. 27 [Heteroatom Analogues of Aldehydes and Ketones (Section ‌27.21.1.5‌27.21.1.5)]}. In aprotic solvents, alkyldiazenolates are stable intermediates that can be isolated as alkali metal salts.[‌82‌–‌84‌] Addition of water causes decomposition. Synthetically useful diazenolate decompositions via nitrogen-separated ion pairs have been developed with alkanediazonium ions not necessarily acting as intermediate species.[‌68‌]

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