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40.4 Product Class 4: N-Haloamines

DOI: 10.1055/sos-SD-040-00600

Wille, U.Science of Synthesis, (200940893.

General Introduction

N-Chloroethanamine was synthesized as long ago as 1881 through a reaction of ethylamine with hypochlorite solution. Nowadays, a range of methods is available for the synthesis of open-chain and cyclic N-haloalkanamines and N-halodialkylamines, including some routes to chiral N-haloaziridines that have a stable configuration at the nitrogen atom. In most cases N-haloamines survive in solution, but in the pure form tend to be thermally labile and decompose upon distillation; indeed, N-fluoroalkanamines, N-fluorodialkylamines, and their precursors are often explosive and should be handled with care. The chemistry of N-halogenated compounds has been reviewed previously;[‌1‌,‌2‌] see also HoubenWeyl, Vol. 16a/2, pp 856893. N-Chloroamines, in particular, attract interest in synthesis as they are used as precursors of N-centered radicals in, for example, the HoffmannLöfflerFreitag reaction[‌3‌] and related procedures,[‌4‌‌13‌] as reagents for aromatic chlorination,[‌14‌‌19‌] and also for the chlorination of alkenes,[‌20‌] alcohols,[‌21‌] and alkanes.[‌22‌] They can also be employed in amination procedures,[‌23‌] as precursors for imines,[‌24‌‌30‌] nitrenium ions,[‌31‌,‌32‌] aziridines,[‌33‌] diaziridines,[‌34‌,‌35‌] and nitrosamines,[‌36‌] as intermediates in the Ruschig reaction,[‌37‌‌39‌] and in some natural product syntheses.[‌39‌‌49‌]

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