Ab-Initio Study of the Base-Promoted Hydrolysis of N-Methylformamide

by Obrien, J. F.; Pranata, J.

The intrinsic reaction coordinate (IRC) pathway for the base-promoted hydrolysis of N-methylformamide in the gas phase has been determined using ab initio molecular orbital calculations at the RHF/6-31+G(d) level of theory. Stationary points were reoptimized at the MP2 level. Along the IRC pathway, the initial process for the reaction is nucleophilic addition of the hydroxide to form a tetrahedral intermediate. The tetrahedral intermediate has to undergo conformational transitions before the reaction can proceed with the elimination step. Two channels for elimination were found; the preferred one leads to methylamide and formate anion, while the other leads to methylamide anion and formic acid. The reactants can also undergo spontaneous proton transfer to form N-methylformamidate anion and water.

Journal
Journal of Physical Chemistry
Volume
99
Issue
34
Year
1995
Start Page
12759-12763
URL
https://dx.doi.org/10.1021/j100034a012
ISBN/ISSN
0022-3654
DOI
10.1021/j100034a012