Naslov
Mechanisms of decomposition of alpha-Hhdroxydialkylnitrosamines in aqeous solutions

Autori
Mesić, Milan ; Peuralahti, Jari ; Blans, Patric ; Fishbein, James C.

Izvornik
Chemical research in toxicology (0893-228X) 13 (2000), 10; 983-992

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
alpha-hydroxydialkylnitrosamines; decomposition; mechanism; aqeous solutions

Sažetak
A study of the decomposition of alpha -hydroxydialkylnitrosamines in aqueous 9 % acetonitrile, with an ionic strength of 1 M (NaClO4), at 25 degreesC is reported. Plots of the logarithm of the buffer-independent rate constant, k(o), against pH are concave up and indicate a three-term rate law for the solvent reaction, including acid (k(H+))-, base (k(OH))-, and PH-independent (K-HOH) terms. Secondary cx-deuterium isotope effects for compound la, (N-nitrosomethylamino)-phenylmethanol, are as follows: k(H)(alpha)//k(D)(alpha) = 1.12 +/- 0.03 and 1.19 +/- 0.02 for k(H+) and koH, respectively. General acid (k(HA)) and general base (k(A)-) catalysis by more acidic carboxylic acid buffers is also observed. Structure reactivity and other parameters obtained in this study, and their changes with substrate and catalyst structure, permit the assignment of mechanisms for the k(H+), k(OH), k(HA), and k(A)- processes.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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