Kinetics and mechanism of imazosulfuron hydrolysis.
Knowledge of the kinetics and pathways of hydrolytic degradation is crucial to the prediction of the fate and transport mechanism of chemicals. This work first describes the kinetics of the chemical hydrolysis of imazosulfuron, a new sulfonylurea herbicide, and evaluates the results to propose a degradation pathway. The hydrolysis of imazosulfuron has been studied in aqueous buffers both within the pH range 1.9-12.3 at ambient temperature (thermostated at 25 +/- 2 degrees C) and at pH 3.6 within the temperature range of 15-55 degrees C. The hydrolysis rate of imazosulfuron was characterized by a first-order kinetics, pH- and temperature-dependent, and accelerated by acidic conditions and higher temperatures. The calculated half-lives at pH 4.5 and 5.9 were 36.5 and 578 days, respectively. At pH 6.6, 7.4, 9.2, and 12.3 no significant change in imazosulfuron concentration was observed after 150 days. Half-lives were much lower at pH <4 (= imazosulfuron pK(a)), at which they ranged from 3.3 to 6.3 days. Moreover, a change in temperature from 15 to 25 degrees C in acidic conditions (pH 3.6) decreased the half-life of imazosulfuron by a factor of approximately 4.0; in any case, a 3-5-fold increase in the rate of hydrolysis was found for each 10 degrees C increase in temperature. In acidic conditions the only hydrolysis products were the two molecules resulting from the cleavage of the sulfonylurea bridge.
Morrica
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P
Dipartimento di Chimica Farmaceutica e Tossicologica, Università degli Studi di Napoli Federico II, Via D. Montesano 49, 80131 Naples, Italy. morrica@unina.it
Barbato
F
F
Della Iacovo
R
R
Seccia
S
S
Ungaro
F
F
D002851:Chromatography, High Pressure Liquid; D006540:Herbicides / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D011725:Pyridines / Q000032:analysis / Q000737:chemistry*; D011743:Pyrimidines / Q000032:analysis / Q000737:chemistry*; D013696:Temperature
D006540:Herbicides; D011725:Pyridines; D011743:Pyrimidines; C433346:1-(2-chloroimidazo(1,2-a)pyridin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea