1-[2-(2,4-二氯苯基)-4-酰氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑的合成及生物活性

2, 4 二氯苯乙酮经溴化得ω 溴 2, 4 二氯苯乙酮,该化合物与丙三醇反应并脱水得 2 (2, 4 二氯苯基 ) 2 溴甲基 4 羟甲基 1, 3 二氧戊环,再在常温下与苯甲酰氯反应合成 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,然后在 130℃与 1H 1, 2, 4 三唑钠反应 36h,所得产物经水解得 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,再在室温以吡啶作缚酸剂,与甲磺酰氯反应 20h,合成 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,最后与各类羧酸的钾盐反应,合成了 10种 1 2 (2, 4 二氯苯基 ) 4 酰氧基甲基 1, 3 二氧戊环 2 基 ]甲基 1H 1, 2, 4 三氮唑类化合物。产物的结构经GC MS、IR证实。对目标产物进行了杀菌活性测定,结果表明,各化合物均具有不同程度的生物活性,其中: 1 2 (2, 4 二氯苯基) 4 (α 甲基苯乙酰氧基)甲基 1, 3 二氧戊环 2 基]甲基 1H 1, 2, 4 三氮唑对水稻稻瘟病菌和油菜菌核病菌的抑制率,分别达到 92 1%与 95 6%,对小麦赤霉病菌和瓜类灰霉病菌的抑制率达到 80%以上;1 2 (2, 4 二氯苯基) 4 对氟苯甲酰氧基甲基 1, 3 二氧戊环 2 基 ]甲基 1H 1, 2, 4 三氮唑对水稻稻瘟病菌和油菜菌核病菌的抑制率分别为 9

Synthesis and Bioactivities of 1-[2-(2,4-Dichlorophenyl)-4-acyloxymethyl-1,3-dioxolan-2-yl] methyl-1H-1,2,4-triazoles

ω-Bromo-2,4-dichloroacetophenone was prepared by bromination of 2,4-dichloroacetophenone,and reacted with glycerol under reflux to give 2-(bromomethyl)-2-(2,4-dichlorophenyl)-4- hydroxymethyl-1,3-dioxolane.This dioxolane reacted with benzoyl chloride at normal temperature to give a benzoate.The benzoate reacted with sodium 1H-1,2,4-triazolyl at 130 ℃ for 36 h,then the obtained product was hydrolyzed to give an important intermediate 1-2-(2,4-dichlorophenyl)-4-hydroxymethyl–1,3-dioxolan-2-yl] methyl-1H-1,2,4- triazole.Finally,reaction of the intermediate with methylsulfonyl chloride followed by reactions with various potassium carboxylates gave ten novel 1-2-(2,4-dichlorophenyl)-4-acyloxymethyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazoles,and their structures were comfirmed by IR spectra and GC-MS spectra.Bioassays showed that all the objective compounds exhibited antifungal activity, especially 1-2-(2,4-dichlorophenyl)-4-(α-methylphenylacetyloxymethyl)-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazole and 1-2-(2,4- dichlorophenyl)-4-p-fluorobenzoyloxymethyl-1,3-dioxolan-2-yl]methyl-1H-1,2,4-triazole,their preventive activity against Pyricularia grisea and Sclerotinia sclerotiorum exceeding 90%.