毒死蜱衍生物的羧基基团能够与蛋白质分子发生酰化或重氮化反应,能够对农药残留快速进行分析检测,在食品安全领域具有潜在应用价值.以三氯硫磷和乙醇为原料,通过醇解,酚羟基、醇羟基亲核取代和三氟乙酸水解4 步反应设计并合成了毒死蜱半抗原衍生物,其结构经1 H NMR,13 C NMR和MS(ESI)表征,并对关键步骤的合成工艺进行优化.结果表明:二氯硫代磷酸乙酯与 3,5,6-三氯-2-吡啶酚的物质的量之比为 1.5∶1.0时,酚羟基亲核取代反应的收率最佳,可达39%.反应中引入4-羟基丁酸叔丁酯后,以4-二甲氨基吡啶为碱,当4-二甲氨基吡啶与O-乙基O-(3,5,6-三氯-2-吡啶基)硫代磷酸的物质的量之比为1.5∶1.0 时,醇羟基亲核取代反应的收率最高,可达22%.当水解底物与三氟乙酸的体积比为3.0∶1.0 时,水解收率最好,可达63%.
Abstract
The carboxyl groups of chlorpyrifos derivatives can acylation or diazotization with protein molecules,which can quickly analyze and detect pesticide residues,and has potential application val-ue in the field of food safety.Chlorpyrifos hapten derivatives were synthesized from thiophosphorus tri-chloride and ethanol by a 4-step reaction of alcoholysis,nucleophilic substitution of phenol hydroxyl and alcohol hydroxyl,and hydrolysis of trifluoroacetic acid.Its structure was characterized by 1 H NMR,13 C NMR and MS(ESI),and the key synthetic process was optimized.The results showed that the yield of phenol hydroxyl nucleophilic substitution was up to 39%when the ratio of ethyl dichlo-rothiophosphate to 3,5,6-trichloro-2-pyridinol was 1.5∶1.0.After tert-butyl 4-hydroxybutyrate was introduced into the reaction,4-dimethylaminopyridine was used as the base,and the yield of the alco-hol hydroxyl nucleophilic substitution reaction was up to 22%when the ratio of the substance amount of 4-dimethylaminopyridine to O-ethyl O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate was 1.5∶1.0.When the volume ratio of hydrolyzed substrate to trifluoroacetic acid was 3.0∶1.0,the hydrolysis yield is preferably up to 63%.
维普
万方数据