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Kinetics and hydrolysis mechanism of chlorsulfuron and metsulfuron‐methyl

机译:氯磺隆和甲磺隆的动力学及水解机理

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AbstractIn acidic media, hydrolysis of chlorsulfuron and metsulfuron‐methyl occurs via two consecutive reactions which were followed by ultraviolet spectrophotometry. For these two reactions, the pseudo‐first‐order rate constants increase proportionally to the concentration of hydronium ion in the more acidic media and to the square of this concentration at higher pH values.A kinetic study by HPLC shows that the first reaction leads to the formation of 4‐methoxy‐6‐methyl‐1,3,5‐triazin‐2‐amine and (o‐chlorophenylsulfonyl) carbamic acid for chlorsulfuron or (o‐methoxycarbonylphenylsulfonyl) carbamic acid for metsulfuronmethyl. The second reaction is the conversion of these sulfonylcarbamic acids to sulfonamides and carbon dioxide. The complete lack of saccharin and of o‐sulfamoyl benzoic acid proves that the ester function of the methoxycarbonyl group is stable.The lack of general acid‐base catalysis and a solvent deuterium isotope effect less than unity are consistent with a rate‐determining cleavage of the protonated substrate.In the basic pH range (10–14) a single reaction occurs, the nucleophilic substitution of the methoxy group on th
机译:摘要 在酸性介质中,氯磺隆和甲磺隆-甲基水解通过两次连续反应发生,然后采用紫外分光光度法。对于这两个反应,伪一级速率常数与酸性介质中水合氢离子的浓度成比例增加,在较高的pH值下与该浓度的平方成比例增加。HPLC的动力学研究表明,第一个反应导致形成4-甲氧基-6-甲基-1,3,5-三嗪-2-胺和(邻氯苯磺酰基)氨基甲酸(氯磺隆)或(邻甲氧羰基苯基磺酰基)氨基甲酸(甲磺隆)。第二个反应是将这些磺酰氨基甲酸转化为磺胺类药物和二氧化碳。完全缺乏糖精和邻氨基磺酰苯甲酸证明甲氧羰基的酯官能团是稳定的。缺乏一般的酸碱催化和溶剂氘同位素效应小于统一性,这与质子化底物的速率决定裂解一致。在碱性pH值范围(10-14)中,发生单个反应,甲氧基在pH范围内发生亲核取代。

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