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Structural effects on the N ‐nitrosation of amino acids
Author(s) -
Gil Rafael,
Casado Julio,
Izquierdo Carmen
Publication year - 1997
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1997)29:7<495::aid-kin3>3.0.co;2-p
Subject(s) - chemistry , nitrosation , intramolecular force , nitroso , carboxylic acid , nitroso compounds , amino acid , kinetics , medicinal chemistry , organic chemistry , biochemistry , physics , quantum mechanics
The relative importance of three different routes for the N‐nitrosationof amino acids (nitrosation by N 2 O 3 , by NO + /NO 2 H 2 + and by intramolecularmigration of the nitroso group from the initially nitrosated carboxylategroup) was investigated for methylaminobutyric acid, methylaminoisobutyricacid, azetidine‐2‐carboxylic acid, azetidine‐3‐carboxylic acid, indolinecarboxylic acid, and phenylaminoacetic acid. Reaction kinetics weredetermined by the initial rate and Guggenheim methods, by spectrophotometricmonitoring of the formation of nitroso amino acid. Kinetic parameterswere calculated using a nonlinear optimization algorithm based on Marquardt'smethod. In the experimental rate equation the dominant term correspondsto nitrosation by dinitrogen trioxide, which experiments at varioustemperatures show to take place via an ordered transition state. Nitrosationby intramolecular migration is significant for substrates facilitatingthe formation of a transition state structure with a 5‐ or 6‐membered ring. © 1997 John Wiley & Sons,Inc. Int J Chem Kinet 29: 495–504, 1997.