Y. Pouilloux et al., SYNTHESIS OF DIMETHYLETHYLAMINE FROM ETHYLAMINE AND METHANOL OVER COPPER-CATALYSTS, Journal of molecular catalysis. A, Chemical, 115(2), 1997, pp. 317-327
The synthesis of dimethylethylamine (DMEA) from monoethylamine (MEA) a
nd methanol was carried out in the presence of a copper chromite type
catalyst. A DMEA yield of 70% was obtained under standard experimental
conditions, the main by-product being diethylmethylamine. A slight in
crease of the basicity without any change in the metallic character of
the catalyst can enhance to 85% of the DMEA formation. Indeed with su
ch a catalyst modification, the rate of the determining steps was chan
ged. By specific experiments involving the reactivity of intermediates
it is demonstrated that the rate of the MEA condensation decreased co
mpared to that of the MEA methylation. Moreover we show that the mecha
nism of the second methylation step which was different from that of t
he first methylation could involve an intermediate formation of an ami
de (MEFA) or of the surface aminoalkoxide. This step depends also on t
he bifunctional character of the modified copper chromite catalyst.