高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (9): 1636-1642.doi: 10.7503/cjcu20160257

• 有机化学 • 上一篇    下一篇

苯环5位取代磺酰脲类化合物的水解动力学及三维定量构效关系初步研究

王美怡1(), 马翼2, 王海英2, 曹刚3, 李正名2   

  1. 1. 北方民族大学化学与化学工程学院, 银川 750021
    2. 南开大学元素有机化学研究所, 天津 300071
    3. 中国科学院上海高等研究院, 上海 201210
  • 收稿日期:2016-04-18 出版日期:2016-09-10 发布日期:2016-08-12
  • 作者简介:联系人简介: 王美怡, 女, 博士, 副教授, 主要从事农药化学和有机化学方面的研究. E-mail:ameiwmy2003@163.com
  • 基金资助:
    国家自然科学基金(批准号: 21262001)资助

Kinetics of the Chemical Hydrolysis and 3D-QSAR Study of 5-Substituted Benzenesulfonylurea Compounds

WANG Meiyi1,*(), MA Yi2, WANG Haiying2, CAO Gang3, LI Zhengming2   

  1. 1. College of Chemistry and Chemical Engineering, Beifang University of Nationality, Yinchuan 750021, China
    2. Research Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China
    3. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
  • Received:2016-04-18 Online:2016-09-10 Published:2016-08-12
  • Contact: WANG Meiyi E-mail:ameiwmy2003@163.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21262001)

摘要:

研究了除草活性较好的9个新型苯环5位取代的磺酰脲类化合物(A~I)分别在酸性、 中性及碱性水溶液中的水解情况. 采用HPLC-MS对水解产物进行分离鉴定, 推测了水解产物的结构及水解路径. 采用比较分子力场(CoMFA)方法, 对化合物的结构与水解半衰期之间的关系进行了三维定量构效关系(3D-QSAR)研究. 结果表明, 苯环5位取代的苯磺酰脲类化合物的水解遵循一级动力学反应, 容易发生酸性条件下的水解, 水解反应第一步主要为酸催化下磺酰脲桥的断裂, 形成5位取代的苯磺酰胺和氨基杂环. 苯环5位取代的苯磺酰胺进一步发生5位酰胺基的水解, 最后得到化合物c(6-氨基糖精)和d(糖精). 苯环5位经修饰改造后, 在相同条件下, 其水解速度明显高于改造前的母体化合物单嘧磺酯和甲磺隆. 苯环5位为酰胺基取代的化合物的水解速度随酰胺基上烷基碳原子数的增加及烷基体积的增大而降低. 经计算所得的CoMFA模型能够对该系列化合物的水解半衰期进行较好的预测.

关键词: 5位取代苯磺酰脲类化合物, 水解, 半衰期, 比较分子力场模型, 三维定量构效关系

Abstract:

The hydrolysis of 9 new 5-substituted benzenesulfonylurea compounds with good herbicidal activity under acidic, neutral and alkaline pH conditions was investigated in laboratory studies. HPLC-MS was used to identify degradates and to study the pathway of hydrolysis. Comparative molecular field analysis(CoMFA) method was applied to the study of the three-dimensional quantitative structure activity relationship(3D-QSAR) on the relationship between the structure of the 5-substituted benzenesulfonylurea compounds and the half-life of hydrolysis. The results showed that the hydrolytic degradation of 5-substituted benzenesulfonylurea followed first-order kinetics. It was easier to be hydrolyzed in acid buffer solutions. Acid-catalyzed cleavage of the sulfonylurea bridge was the first step of degradation, and thus produces 5-substituted benzene sulfonamide and amino-heterocyclic. Amide group further hydrolyzed producing the compound c(6-amino saccharin) and d(saccharin). The 5-substituted benzenesulfonylurea compounds hydrolyzed significantly faster than the parent compounds, Monosulfuron-methyl and Metsulfuron-methyl, under the same conditions. The hydrolysis rate decreased with the increase of the number of alkyl carbon atoms on the amide group and the increase of the volume of the alkyl group. The CoMFA model was able to predict the hydrolysis half-life of this series of compounds.

Key words: 5-Substituted benzenesulfonylurea compound, Hydrolysis, Half-life, Comparative molecular field analysis(CoMFA) model, Three-dimensional quantitative structure activity relationship(3D-QSAR)

中图分类号: