Science of Synthesis

Kubik, S., Science of Synthesis, (2010) 41, 510.

Nitrosation of aliphatic amines in basic aqueous solution (pH 9–11) can be achieved by the reaction with pentacyanonitrosylferrate(III) salts [e.g., Na2Fe(CN)5NO, “sodium nitroprusside”] in the absence of air.[‌27‌–‌29‌] Decomposition of the reagent occurs if the pH of the solution exceeds 13. Diazonium compounds are obtained with primary aliphatic amines and N-nitrosoamines with secondary aliphatic amines. Tertiary aliphatic and aromatic amines are largely inert. The reaction involves initial addition of the amine to the coordinated nitric oxide. The resulting complex reacts either directly with a second equivalent of the amine releasing the N-nitrosoamine, which decomposes to give a diazonium hydroxide, or loses water yielding a diazonium ion complex that is cleaved by another molecule of amine (‌Scheme 6‌).[‌27‌] In both cases, 2 equivalents of the amine are consumed per mole of complex. If the reaction is carried out in the presence of air, small amounts of oxidized products are formed. The product composition observed upon deamination of a primary amine with pentacyanonitrosylferrate(III) at basic pH is similar to the one resulting from diazotization with nitrous acid at low pH.[‌29‌]

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