1-[2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑类化合物的合成及杀菌活性研究

2,4-二氯苯乙酮经溴化得ω-溴-2,4-二氯苯乙酮,该化合物与丙三醇在对甲基苯磺酸催化下脱水,得2-(2,4-二氯苯基)-2-溴甲基-4-羟甲基-1,3-二氧戊环,该中间体与苯甲酰氯在常温下反应,合成了2-(2,4-二氯苯基)-2-溴甲基-4-苯甲酰氧基甲基-1,3-二氧戊环,然后与三氮唑钠盐在130℃反应36 h,之后在碱性条件下水解,获得1-2-(2,4-二氯苯基)-4-羟甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,再以吡啶为缚酸剂继续与甲磺酰氯反应,合成了1-2-(2,4-二氯苯基)-4-甲磺酰氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,最后在碱性条件下,与12个不同结构的酚缩合成标题化合物1-2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑。标题化合物的结构用GC-MS、FTIR进行了表证。生物活性实验结果表明,12个标题化合物对水稻稻瘟病菌的抑菌率均在88.0%以上,其中,1-2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑达100%。1-2-(2,4-二氯苯基)-4-苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑和1-2-(2,4-二氯苯基)-4-对硝基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对油菜菌核病菌的抑菌率分别为100%和97.8%;1-2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对小麦赤霉病菌的抑制活性为91.2%。

Synthesis and Antifungal Activities of 1- [ 2- ( 2,4-Dichlorophenyl ) -4- alkoxymethyl-1,3-dioxolan-2-yl ] methyl-1H-1,2,4-triazoles

ω-Bromo-2,4-dichloroacetophenone,synthesized by bromination of 2,4-dichloroacetophenone,reacted with glycerol in the presence of p-toluenesulfonic acid to give 2-(2,4-dichlorophenyl)-2-bromomethyl-4-hydroxymethyl-1,3-dioxolane,which then reacted with benzoyl chloride in normal temperature to give 2-(2,4-dichlorophenyl)-2-bromomethyl-4-benzoyloxymethyl-1,3-dioxolane.This compound in turn reacted with sodium 1H-1,2,4-triazolyl at 130 ℃ for 36 h and then dissolved in sodium hydroxide solution to give 1-2-(2,4-dichlorophenyl)-4-hydroxymethyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazole,which further reacted with methylsulfonyl chloride to give the intermediate 1-2-(2,4-dichlorophenyl)-4-methylsulfonyloxymethyl-1,3-dioxolan-2-yl] methyl-1H-1,2,4-triazole.At last 12 objective compounds 1-2-(2,4-dichlorophenyl)-4-alkyloxymethyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazoles were synthesized by reaction of this intermediate with 12 different phenols under alkaline condition.Their structures were confirmed by FTIR and GC-MS.Results of biological screening show that all the 12 objective compounds have high biological activities.Their antifungal activities against Pyricularia oryzaeare are all higher than 88.0%,and 100% with 1-2-(2,4-dichlorophenyl)-4-(m-methylphenoxy)methyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazole.Compounds 1-2-(2,4-dichlorophenyl)-4-phenoxymethyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazole and 1-2-(2,4-dichlorophenyl)-4-(p-nitrophenoxy)methyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-trazole have 100% and 97.8% antifugal activities against Sclerotinia sclerotiorum respectively.1-2-(2,4-Dichlorophenyl)-4-(m-methylphenoxy)methyl-1,3-dioxolan2-yl]methyl-1H-1,2,4-trazole has 91.2% antifugal activity against Fusarium graminearum.