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Full Paper
Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by in situ Generated Hydroxide Ion: A Mechanistic Consideration
Article first published online: 9 FEB 2010
DOI: 10.1002/adsc.200900699
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Kim, D. W., Huh, E. S., Park, S. D., Nguyen, L. V., Nguyen, M. D., Kim, H. S., Cheong, M. and Nguyen, D. Q. (2010), Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by in situ Generated Hydroxide Ion: A Mechanistic Consideration. Adv. Synth. Catal., 352: 440–446. doi: 10.1002/adsc.200900699
Publication History
- Issue published online: 17 FEB 2010
- Article first published online: 9 FEB 2010
- Manuscript Received: 8 OCT 2009
Funded by
- Carbon Dioxide Reduction & Sequestration Research Center. Grant Number: AC3-101
Keywords:
- 1,6-di(methyl carbamate)hexane;
- dimethyl carbonate;
- isocyanates;
- methoxycarbonylation;
- non-phosgene process
Abstract
The methoxycarbonylation reactions of aliphatic diamines with dimethyl carbonate are accelerated greatly in the presence of water. Theoretical investigations on the mechanistic aspects of the methoxycarbonylation of 1,6-hexanediamine strongly suggest that the hydroxide ion, generated in situ from the interaction of 1,6-hexanediamine with water, is an active catalytic species and plays a pivotal role in the rate-determining hydrogen abstraction step from the amino group.