环己二酮类除草剂的绿色合成研究
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摘要
本文在查阅文献的基础上,对农药作用及发展做了概述,并对除草剂的历史及研究现状做了重点分析,进而对环己二酮类除草剂磺草酮和硝草酮进行了较为详细的综述,研究了合成方法、物化性质、作用机制及毒性等。
在此基础上对磺草酮和硝草酮的合成路线进行了选择和优化。采用对甲基苯磺酰氯为起始原料,先通氯气氯化制备3-氯-4-甲基苯磺酰氯,然后经亚硫酸钠、碳酸氢钠和氯乙酸钠共同作用发生还原烷基化反应生成3-氯-4-甲基苯甲砜;以对甲基苯磺酰氯为起始原料,先还原烷基化制备对甲基苯甲砜,然后混酸硝化得到3-硝基-4-甲基苯甲砜。3-氯-4-甲基苯甲砜和3-硝基-4-甲基苯甲砜分别采用空气氧化法及硝酸氧化法制备2-氯-4-甲砜基苯甲酸和2-硝基-4-甲砜基苯甲酸,然后经固体三光气酰化得到2-氯-4-甲砜基苯甲酰氯和2-硝基-4-甲砜基苯甲酰氯,再和1,3-环己二酮在缚酸剂碳酸钾、重排剂丙酮氰醇作用下以乙腈为溶剂,缩合重排生成磺草酮和硝草酮原药。
本文通过试验,确定了较佳的磺草酮和硝草酮的合成路线,并对部分反应步骤进行优化,采用了绿色合成方法,提高了反应收率,而且工艺路线切实可行。
The function and development of pesticide were reviewed in this peaper.The history and present situation of herbicide were summarized, then sulcotrione and mesotrione which were cyclohexanedione-type herbicides were summarized about their synthetic routes,physical and chemical property,action mechanics and toxicity etc with more than ninety references.
Based on references,the synthetic routes of sulcotrione and mesotrione were picked out and optimized.3-chloro-4-methyl-methylsulfonylbenzene, an intermediate of sulcotrione,was synthesized using 4-methylbenzenesulfonyl chloride as a primary material,followed by chlorination with chlorine,reduction with sodium carbonate and sodium sulfite,alkylation with sodium chloroacetate.3-nitro-4-methyl-methylsulfonylbenzene, an intermediate of mesotrione,also was synthesized using 4-methylbenzenesulfonyl chloride as a primary material,but firstly by reduction and alkylation,then nitration with mixed acid.3-chloro-4-methyl-methylsulfonylbenzene and 3-nitro-4-methyl-methylsulfonylbenzene were oxidated by air or nitric acid to prepare 2-chloro-4-(methylsulfonyl)benzoic acid and 2-nitro-4-(methylsulfonyl)benzoic acid which were acylated with BTC to obtain 2-chloro-4-(methylsulfonyl)benzoyl chloride and 2-nitro-4-(methylsulfonyl)benzoyl chloride.After that,the chloride reacted with 1,3-cyclohexanedione in the presence of potassium carbonate as acid acceptor and acetone cyanohydrin as rearrangement catalyst to carry out the condensation and rearrangement reactions to obtain sulcotrione and mesotrione at last.
Through the experimentation,an optimum synthetic route of sulcotrione and mesotrione was chosen,and some.steps were optimized by green method.The route was suitable for industrial production.
在此基础上对磺草酮和硝草酮的合成路线进行了选择和优化。采用对甲基苯磺酰氯为起始原料,先通氯气氯化制备3-氯-4-甲基苯磺酰氯,然后经亚硫酸钠、碳酸氢钠和氯乙酸钠共同作用发生还原烷基化反应生成3-氯-4-甲基苯甲砜;以对甲基苯磺酰氯为起始原料,先还原烷基化制备对甲基苯甲砜,然后混酸硝化得到3-硝基-4-甲基苯甲砜。3-氯-4-甲基苯甲砜和3-硝基-4-甲基苯甲砜分别采用空气氧化法及硝酸氧化法制备2-氯-4-甲砜基苯甲酸和2-硝基-4-甲砜基苯甲酸,然后经固体三光气酰化得到2-氯-4-甲砜基苯甲酰氯和2-硝基-4-甲砜基苯甲酰氯,再和1,3-环己二酮在缚酸剂碳酸钾、重排剂丙酮氰醇作用下以乙腈为溶剂,缩合重排生成磺草酮和硝草酮原药。
本文通过试验,确定了较佳的磺草酮和硝草酮的合成路线,并对部分反应步骤进行优化,采用了绿色合成方法,提高了反应收率,而且工艺路线切实可行。
The function and development of pesticide were reviewed in this peaper.The history and present situation of herbicide were summarized, then sulcotrione and mesotrione which were cyclohexanedione-type herbicides were summarized about their synthetic routes,physical and chemical property,action mechanics and toxicity etc with more than ninety references.
Based on references,the synthetic routes of sulcotrione and mesotrione were picked out and optimized.3-chloro-4-methyl-methylsulfonylbenzene, an intermediate of sulcotrione,was synthesized using 4-methylbenzenesulfonyl chloride as a primary material,followed by chlorination with chlorine,reduction with sodium carbonate and sodium sulfite,alkylation with sodium chloroacetate.3-nitro-4-methyl-methylsulfonylbenzene, an intermediate of mesotrione,also was synthesized using 4-methylbenzenesulfonyl chloride as a primary material,but firstly by reduction and alkylation,then nitration with mixed acid.3-chloro-4-methyl-methylsulfonylbenzene and 3-nitro-4-methyl-methylsulfonylbenzene were oxidated by air or nitric acid to prepare 2-chloro-4-(methylsulfonyl)benzoic acid and 2-nitro-4-(methylsulfonyl)benzoic acid which were acylated with BTC to obtain 2-chloro-4-(methylsulfonyl)benzoyl chloride and 2-nitro-4-(methylsulfonyl)benzoyl chloride.After that,the chloride reacted with 1,3-cyclohexanedione in the presence of potassium carbonate as acid acceptor and acetone cyanohydrin as rearrangement catalyst to carry out the condensation and rearrangement reactions to obtain sulcotrione and mesotrione at last.
Through the experimentation,an optimum synthetic route of sulcotrione and mesotrione was chosen,and some.steps were optimized by green method.The route was suitable for industrial production.
引文
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