Selective Synthesis of Trimethylamine by Catalytic N‐Methylation of Ammonia and Ammonium Chloride by utilizing Carbon Dioxide and Molecular Hydrogen

The synthesis of trimethylamine (TMA) through a multicomponent combination of ammonia with carbon dioxide and molecular hydrogen by using a homogeneous ruthenium catalyst was explored. The use of [Ru(triphos)(tmm)][triphos: 1,1,1-tris-(diphenylphosphinomethyl)ethane, tmm: trimethylene methane] together with aluminum trifluoromethanesulfonate as a co-catalyst resulted in high ammonia conversion and excellent selectivity for TMA in organic solvents. Aqueous solutions of ammonium chloride were methylated almost quantitatively to the corresponding hydrochloride salt (i.e., TMA center dot HCl) in a biphasic solvent system by using the same Ru complex without the need for any co-catalyst.