Interactions of halogens with amines

Mann, Warren Charles (1974) Interactions of halogens with amines. PhD thesis, Thames Polytechnic.

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Abstract

The individual stages of the interaction of amines with halogens - in particular, iodine - have been studied. 'In the course of this investigation, it has been shown that amines and iodine interact initially via the nitrogen lone pair to form molecular complexes (CHARGE-TRANSFER COMPLEXES). Several of these have been isolated and some of their properties studied in detail. It was thus determined that these complexes can undergo further chemical change during which the hydrogen iodide which is generated converts any unreacted amine to the corresponding hydroiodide salt. The latter is inert to oxidation by iodine under the conditions employed. It has been shown that this mode of reaction is dependent upon the availability of a-aliphatic hydrogen in the amine molecule.

The initial oxidation product derived from the amine is the corresponding IMMONIUM SALT. This intermediate may, according to reaction conditions, undergo hydrolysis to secondary amine and carbonyl compound or conversion to ENAMINE; the latter may then undergo further transformation by inter- or intramolecular reaction.

The nature of the products isolated from the oxidation of several amines by iodine in isopropanol solution has been rationalised in terms of this generalised reaction pathway, which is analogous to those proposed by other workers for the oxidation of amines by other two-electron oxidants.

This reaction pathway also applies to the formation of an industrial disinfectant by the action of solid iodine on a commercially available tertiary amine mixture. It was thus demonstrated that most of the amine used is recovered from the reaction mixture as the base hydroiodide and that the hydrogen iodide needed for this conversion is formed during the degradative oxidation of a minor proportion of the starting material.

Furthermore, it has been established that the biocidal principle of the commercial disinfectant formulation is the N-alkyldiethanolamine hydriodide. A concurrent study of the effect of structure on biological activity has confirmed the dependence of disinfectant activity on detergent properties in this class of disinfectants.

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