Study On Synthesis And Bioactivity Of 1-[2-(2,4-Dichlorophenyl)-4-(Oxymethyl)-1,3-Diox Olan-2-Yl Methyl]-1,2,4-Triazole

Triazoles with structure of 1-(2-aryl-1,3-dioxolan-2-ylmethyl)-1-H-1,2,4triazole ring is one important kind of fungicide. For example, Etaconazole is widely used in the treatment of fungicide of woods. Propiconnazole was used to cure field fungal. Research results show that the bioactivities of compounds l-[-2-(2,4-Dichloro- phenyl) -4-oxyl-l,3-dioxolan-2-yl]methyl-l,2,4-triazole have obvious difference when 4-position of alkyl group differ. Deconazole and Itraconazole, having the same structure, are excellent and widely used in the treatment of significant fungal infections. But there haven't any analogy compounds was used as pesticide reported by now.In this paper, The compound of1-[-2-(2,4-Dichlorophenyl)-4-(oxymethyl) -1,3-dioxolan-2-yl]methyl-l,2,4-triazole was used as intermediate. And 4-position of methylol was displaced by oxyl group or acyloxy group through reaction of esterifing and etherifing. Twenty-two compounds of triazole derivatives were successfully synthesized, some ester compounds and some ether compounds. Bioactivities of twenty compounds were screened.The synthesis was performed using 2.4-Dichloroacetophenone as starting material. Successful synthesizing the intermediate through three routes. The first route was carried out by bromating, dehydrating, replacing reaction. The second route was carried out by bromating, dehydrating, benzoylating, hydrolysizing reaction and the third by dehydrating ,bromating, benzoylating, hydrolysizing reaction. Using A12O3 as catalyst in the first route can obviously improve the yield. In the second route and third route, the insertion of benzoylation can effectively protect the active methylol radical and may advantageously be employed to facilitate the separation of cis- and trans-forms of the intermediate.The ketal ring structure in the intermediate of 1-[-2-(2,4-Dichlorophenyl) -4-(oxy-methyl)-1,3-dioxolan-2-yl]methyl-1,2,4-triazole would easily decompose in acid condition. So the acidic catalyst is excepted in esterification. More over, it is difficult to esterify by acyl chloride because the structure of 1,2,4-triazole ring can bind acid or acyl chloride, producing binding-salt. But the compound mehane sulfonyl chloride can esterify the intermediate smoothly for it's not so active. The intermediate 1 -[-2-(2,4-Dichlorophenyl)-4-methylsulfonyl -methyl-1,3-dioxolan-2-yl]methyl-1,2,4-t riazole is very active. That can easily react with sodium alcholate, phenate, and acidic sodium. The aimed compounds were ester and ether(10 esters and 12 ethers). Procedure carried out to synthesize ester compounds presented in this paper has not been reported before. Moreover, the ether compounds differ from those in patens.The structures show as follow:CI,CIAfter purified, 22 compounds are analyzed and verified by HPLC, GC- MS, FT-IR, NMR.According to structure-activity relationship, 20 compounds were used for general bioactivity screening of fungicidal activity, according to the procedure of SOP. Most of the aimed compounds exhibited fungal growth inhibition activity and selectivity on 6 sorts of fungals be treated.The whole samples show high activity to piricularia. Compounds Z-02, Z-07, M-01,M-06, M-09, M-11 have high activity to Sclerotinia; M-01 has high activity to Plasmopara; compounds Z-01, Z-06, M-01, M-08, M-09 have high activity to Erysiphe gramins de Candolle.According to the results of screening, we make the conclusion that the bioactivity of ester compounds is higher than ether compounds. The research results show that Electronegativity of 4-position R group has negative correlation to it's bioactivity.