Synthesis And Biological Activity Of Acrylpimaric Acid-based Disulfamide-thiadiazole And Diamide-thiadiazole Compounds

Rosin is an abundant,renewable,and natural resource of China.Resin acids in rosin and their derivatives exhibit a wide range of bioactivities.In recent years,it has become one of the research focuses for chemistry of forest product and natural organic chemistry to synthesize bioactive compounds through structural modification of resin acids in rosin.In this thesis,acrylpimaric acid was prepared by Diels-Alder cycloaddition reaction of rosin with acrylic acid at first.Then,two types of novel acrylpimaric acid-based five-membered heterocyclic compounds with potential bioactivity,were designed and synthesized by modification of two carboxyl groups in acrypimaric acid,and by introduction of bioactive 1,3,4-thiadiazole,sulfonamide,and amide groups into the molecular skeleton of acrylpimaric acid.This study aims at providing a new way for the deep processing and utilization of rosin.In this thesis,acrylic modified rosin was prepared by Diels-Alder cycloaddition reaction of rosin with acrylic acid under high temperature,from which acrylpimaric acid 1 was separated and purified.Then,the intermediate acrylpimaric acid-based dithiadiazole 2 was prepared by the reaction of acrylpimaric acid with thiosemicarbazide in the presence of phosphorus oxychloride as dehydrating agent,followed by the N-acylation reaction of the intermediate 2 with substituted benzene sulfonyl chlorides to afford eight novel acrylpimaric acid-based disulfamide-thiadiazole compounds 3a-3h.Furthermore,seven novel acrylpimaric acid-based diamide-thiadiazole compounds 4a-4g were synthesized by the N-acylation reaction of the intermediate 2 with substituted benzoyl chloride.The synthetic conditions were investigated preliminarily,and all the target compounds were characterized and analyzed by means of FT-IR,1H NMR,and 13C NMR.The fungicidal activity of the intermediate acrylpimaric acid-based dithiadiazole 2 and all the target compounds against Physalospora piricola,lternaria solani,Fusarium oxysporum f.cucumerinum,ibberella zea,and ercospora arachidicola was tested by agar well diffusion method.The results showed that acrylpimaric acid-based disulfamide-thiadiazole compounds 3a-3h exhibited a certain inhibition activity against the above-mentioned five fungi at the concentration of 50 ?g·mL-1,especially against Physalospora piricola,in which compound 3e(R=4-Cl)had the best inhibition rate of 67.1%against Physalospora piricola.Compound 3a(R=4-H)showed inhibition rate of 55.5%against Fusarium oxysporum f.cucumerinum.Acrylpimaric acid-based diamide-thiadiazole compounds 4a-4g showed a certain inhibition activity against the above-mentioned five fungi,especially against Physalospora piricola,in which compound 4g(R=2-Cl)had the best inhibition rate of 60.0%against Physalospora piricola.Compound 4c(R=4-F)showed inhibition rate of 51.7%against Alternaria solani.The intermediate acrylpimaric acid-based dithiadiazole 2 displayed inhibition activity of 74.3%(B-class activity level)against Physalospora piricola.The herbicidal activity of the intermediate acrylpimaric acid-based dithiadiazole 2 and all the target compounds was evaluated by barnyard grass beaker method and rape petri dish method.It was found that,at the concentration of 100 ?g·mL-1,only several acrylpimaric acid-based disulfamide-thiadiazole compounds 3a-3h diaplayed weak inhibition activity agaist root of rape(Brassica campestris)and barnyard grass(Echinochloa crusgalli(L.)).Most of the acrylpimaric acid-based diamide-thiadiazole compounds 4a-4g showed good growth inhibition activity against root of rape(Brassica campestris),in which compound 4e(R=4-Br)had the best inhibition rate of 92.4%(A-class activity level),and compounds 4b(R=4-CH3)and 4d(R=4-Cl)had inhibition rates of 77.4%and 73.2%(B-class activity level),respectively.All the compounds 4a-4g displayed weak growth inhibition activity against barnyard grass(Echinochloa crusgalli(L.)).Besides,the intermediate 2 exhibited inhibition activity of 63.1%(B-class activity level)against root of rape(Brassica campestris)at the concentration of 100 ?g·mL-1.