The Kinetics and mechanism of the acid-catalysed chlorination of olefins by N-chloromorpholine

Abstract

The acid-catalysed chlorination of allyl ethyl ether by N-chloromorpholine has been studied. The rates of these reactions have been measured and that catalysed by hydrochloric acid is faster than that catalysed by perchloric acid at the same concentration. Suitable theoretical explanations have been sought to account for these observations. From a consideration of the products isolated and the observed kinetics, plausible mechanisms have been postulated. These alternative mechanisms are discussed critically in the light of the experimental evidence available. In the case of the perchloric acid reaction, chlorination is thought to proceed via the chloromorpholinium ion, but in hydrochloric acid the reaction also occurs through the agency of an intermediate involving chloride ions. The nature of this intermediate is discussed and new methods of analysing the kinetic data are suggested.