Studies into reactions of N-methylmorpholine-N-oxide (NMMO) and its hydrates with cyanuric chloride

Article abstract of DOI:10.1016/S0040-4020(02)01291-7

The course of the reaction between N-methylmorpholine-N-oxide (NMMO, 1a) and cyanuric chloride (2) is strictly dependent on the hydrate water content of the amine oxide. In solid phase, both substances undergo an explosion-like, extremely exothermic reaction. In solution, this process becomes controllable and leads to a quantitative degradation of NMMO into morpholine and formaldehyde, with 2 only acting as an inducing agent. The reaction can be conducted in a way that a clean deoxygenative demethylation is achieved. The monohydrate of NMMO (1b) is quantitatively converted into N-methylmorpholine and hypochlorous acid by the action of 2. This conversion can be used in synthesis either to deoxygenate tertiary amine N-oxide monohydrates, or to produce chlorohydrins in non-aqueous, organic media in superior yields. The semisesquihydrate of NMMO (1c) reacts with 2 under consumption of water until non-hydrated NMMO is present, which is then further converted into morpholine and HCHO, as in the case of 1a being directly employed as the starting material.