Modeling the reaction mechanisms of the imide formation in an N-(o-carboxybenzoyl)-L-amino acid.
Reaction mechanisms of the imide formation in an N-(o-carboxybenzoyl)-l-amino acid have been studied using density functional theory. Our results suggest that the reaction route initiated by protonation at the oxygen of the carboxyl group of the amino acid is favored, while those initiated by deprotonation at the oxygen of the carboxyl group of phthalic acid and at the amidic nitrogen are minor pathways. During the dehydration process, water functions as a catalyst. These conclusions are in good agreement with the experimental facts that at highly acidic conditions (hydrogen ion concentration H(0) < -1), imide formation is the most favorable pathway, whereas in the pH range 0-5, cyclization to the imide is not the dominant reaction. Our calculations also show that the carboxyl group of the amino acid is involved in the catalytic reaction in both the favored and minor pathways and that solvent effects have little influence on the reaction barriers.
Wu
Zhijian
Z
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3 Canada.
Ban
Fuqiang
F
Boyd
Russell J
RJ
D000596:Amino Acids / Q000737:chemistry* / Q000378:metabolism; D016282:Aspartic Acid Endopeptidases / Q000737:chemistry* / Q000378:metabolism; D005998:Glycine / Q000031:analogs & derivatives*; D008956:Models, Chemical; D008968:Molecular Conformation; D013816:Thermodynamics
D000596:Amino Acids; D016282:Aspartic Acid Endopeptidases; D005998:Glycine