Synthesis And Biological Activity Of Acrylpimaric Acid-based Dihydrazide And Dithiadiazole Compounds

Rosin is a renewable non-wood forest product,as well as a natural and preponderant resource of China.Resin acids in rosin and their derivatives show a wide range of biological activities.In recent years,it has become one of the research focuses for natural organic chemistry to synthesize bioactive compounds through structural reform of resin acids in rosin.In this thesis,acrylpimaric acid was prepared by reaction of rosin with acrylic acid,then two types of novel acrylpimaric acid-based derivatives with potential biological activity,acrylpimaric acid-based diacylhydrazone and acrylpimaric acid-based dithiadiazole,were designed and synthesized by modification of two carboxyl goups in structure of acrylpimaric acid and introduction of acylhydrazone and thiadiazole active groups into the structure of acrylpimaric acid.This study aims at providing a new pathway for deep procesing and utilization of rosin.In this thesis,acrylpimaric acid 1 was separated and purified from acrylic modified rosin which was prepared by Diels-Alder cycloaddition reaction of rosin with acrylic acid under high temperature,and converted into its dichloride 2.Then,acrylpimaric acid dihydrazide 3 was prepared by reaction of acrylpimaric acid dichloride 2 with hydrazine hydrate,followed by condensation reaction of acrylpimaric acid dihydrazide 3 with substituted phenyl aldehydes to afford eleven novel acrylpimaric acid-based diacylhydrazone compounds 4a-4k.Furthermore,eight novel acrylpimaric acid-based dithiadiazole compounds 6a-6h were synthesized N-acylation reaction of acrylpimaric acid dichloride 2 with 2-amino-5-substituted phenyl-1,3,4-thiadiazoles 5a-5h.The synthetic conditions were investigated preliminarily,and the target compounds were characterized by means of FT-IR,ESI-MS,1H NMR,and 13C NMR.The fungicidal activity of all the target compounds was evaluated by agar well diffusion method against Fusarium oxysporum f.cucumerinum,Physalospora piricola,Alternaria solani,Cercospora arachidicola,and Gibberella zea.It was found that,at the concentration of 50 μg·mL-1,acrylpimaric acid-based diacylhydrazone compounds 4a-4k exhibited a certain inhibitory activity against all the five tested fungi,in which most of the compounds had inhibition rates of ≥50.0%against Physalospora piricola,and compound 4i(R=m-OCH3)had inhibition rate of 57.1%against Physalospora piricola.Compound 4d(R=o-Cl)had inhibition rate of 65.5%against Fusarium oxysporum f.cucumerinum.Acrylpimaric acid-based dithiadiazole compouds 6a-6h exhibited a certain inhibitory activity against the other four tested fungi except for Alternaria solani,in which most of the compounds had inhibition rates of>50.0%against Physalospora piricola,and compounds 6c(R=p-F),6d(R=m-Cl),and 6e(m-CH3)had the same inhibition rate of 66.9%against Physalospora piricola.In which compounds 6c(R=p-F),6d(R=m-Cl)and 6e(R=m-CH3)had the best inhibition rate of 66.9%,66.9%and 66.9%against Fusarium oxysporum f,cucumerinum,respectively.Compound 6d(R=m-Cl)had the best inhibition rate of 57.8%and 52.9%against Cercospora arachidicola,and Gibberella Zeae,respectively.Besides,compound 6d(R=m-Cl)displayed the best inhibition rates of 66.9%,57.8%,and 52.9%against Physalospora piricola,Cercospora arachidicola,and Gibberella Zeae,respectively,implying that this compound is a leading compound worthy of being studied deeply.The herbicidal activity of all the target compounds was evaluated by rape petri dish method and barnyard grass beaker method.It was found that,at the concentration of 100 μg·mL-1,acrylpimaric acid-based diacylhydrazone compounds 4a-4k and acrylpimaric acid-based dithiadiazole compouds 6a-6h exhibited almost no growth inhibition activity against root of rape(Brassica campestris).Also,only part of the two types of compounds displayed weak growth inhibition activity against barnyard grass(Echinochloa crusgalli(L.)).The plant growth regulating activity of all the target compounds was evaluated by cucumber cotyledon expansion method and wheat coleoptile section elongation method.evaluated.The results showed that,at the concentration of 10 μg·mL-1,all the target compounds exhibited a certain cytokinin and auxin activity,in which compounds 6g(R=m-NO2)and 6f(R=p-CH3)had the best cytokinin activity of 23.2%(promotion)and-16.5%(inhibition),respectively,and compounds 4c(R=p-F)and 6b(R=m-F)had the best auxin activity of 19.7%(promotion)and-12.1%(inhibition),respectively.