Do alkylhydroxylamines form N-nitrosamines?

Usual secondary amines can form *N*-nitrosamines with nitrosating agents, *e.g.*, $\ce{KNO2}$, and are therefore forbidden in metalworking fluids.


But can alkylhydroxylamines form *N*-nitrosamines with nitrosating agents in metalworking fluids?


I assume the basicity of the *N*-atom in alkylhydroxylamines is lowered by the inductive effect and the mesomeric effect. But is this enough to prevent formation of *N*-nitrosamines?




Yes they can in acidic solutions according to the abstract of this paper$^{[1]}$:



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> *O*-Alkylhydroxylamines react with nitrous acid with a rate law $v = k\_2\ce{[R^1NH2^+OR^2][HNO2]}$; the mechanism involves electrophilic nitrosation at the nitrogen atom of the free base. At acid concentrations below $\pu{2M}$-per-chloric acid, hydroxylamine and *N*-methylhydroxylamine react with nitrous acid by an acid-catalysed mechanism with a rate law $v = k\_3\ce{[RNH2^+OH][HNO2]}h\_\circ$; this involves initial nitrosation at the oxygen atom of the conjugate acid, followed by migration of the nitrosonium ion to the nitrogen. At higher acidities the *O*-nitrosation can be reversed, and the migration of the nitrosonium ion becomes the rate-determining stage.
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**Reference**


1. T. D. B. Morgan, G. Stedman, M. N. Hughes, "Kinetics and mechanism of the reaction between nitrous acid and hydroxylamine," *J. Chem. Soc. B* **1968**, 344-349 (DOI: <https://doi.org/10.1039/J29680000344>).


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