N-Methylhydroxylamine hydrochloride

The substance appears as white to almost white crystals or crystalline powder. It exhibits solubility in water.

N-Methylhydroxylamine hydrochloride is used as an inorganic catalyst used in the transamidation of primary amides with amines. It is employed in constructing hydroxamates, important functional groups for the complexation of iron.

N-methylhydroxylamine hydrochloride (N-MHA) was synthesized by a high pressure catalytic hydrogenation method using noble metal Pd/C and Pt-Rh/C as the catalyst. During the synthesis process, the catalyst was easily poisoned and the products would be deeply reduced to methylamine. Therefore, the purity of N-MHA is low and the cost is high. An industrial electrolytic cell was designed for the electrochemical synthesis of N-methylhydroxylamine hydrochloride (N-MHA). Copper was used as the cathode, graphite as the anode, and a cation membrane as the separator. The results show that N-MHA with a high purity of 99% can be electrosynthesized directly from nitromethane in HCl solution.

N-methylhydroxylamine hydrochloride was widely used in the 1,3-dipolar cycloaddition and N-methylation reaction. For example, it has been considered an extremely important intermediate in the synthesis of biological active azetidinone and isoxazole compounds such as piperylone, isopyrine, and muscimole.

[1] A. Gibson and S. Mirzazadeh. N-methylhydroxylamine inhibits and M&B 22948 potentiates relaxations of the mouse anococcygeus to non-adrenergic, non-cholinergic field stimulation and to nitrovasodilator drugs.British Journal of Pharmacology.1989, 96    637-644.  DOI:10.1111/j.1476-5381.1989.tb11863.x
[2] J. R. Ochoa Gomez. Electrosynthesis of N-methylhydroxylamine.Journal of Applied Electrochemistry.1991, 21     331-334. DOI:10.1007/BF01020218
[3] Reacts with aldehydes and ketones to give nitrones, which undergo 1,3-dipolar addition reactions with alkenes. Cycloaddition to trimethylvinylsilane has been used in a 2-carbon extension of aldehydes to ɑ-unsaturated aldehydes: J. Org. Chem., 49, 3421 (1984). DOI:10.1021/jo00192a047
[4] Intramolecular cycloaddition has been used as a route to bicyclic systems, e.g. from citronellal: Org. Synth. Coll., 6, 670 (1988).
[5] Reviews: 1,3-Dipolar cycloadditions of nitrones: Synthesis, 205 (1975). The [3+2] nitrone-olefin cycloaddition reaction: Org. React., 36, 1 (1988). Synthetic applications of nitrones: Org. Prep. Proced. Int., 17, 25 (1985).
[6] For conversion to, and reactions of, the N,O-bis(TMS) derivative, see: J. Chem. Soc., Perkin 1, 1823 (1989).
[7] GAN Y, WENKUI Z, HUANG H, et al. Industrial Synthesis of N-Methylhydroxylamine Hydrochloride by Electrochemical Reduction of Nitromethane[J]. Chinese Journal of Chemical Engineering, 2006, 14: 649-653. DOI:10.1016/S1004-9541(06)60129-8.