Synthesis And Biological Activity Of Maleated Rosin-based Disulfamide And Dithiourea Compounds

Rosin is a very abundant,renewable,and rtatural resource of China.Resin acids in rosin and their derivatives show a wide range of bioactivity.In recent years,it has become one of the research focuses for synthetic organic chemistry and natural organic chemistry to synthesize bioactive compounds through structural modification of resin acids in rosin.In this thesis,maleated rosin was prepared by the reaction of rosin with maleic anhydride,and two types of maleated rosin-based derivatives with potential biological activites,maleated rosin-based disulfamides and maleated rosin-based dithioureas,were designed and synthesized.This research aims at providing a new way for deep processing and utilization of rosin.In this thesis,maleated rosin 1 was prepared by the Diels-Alder reaction of rosin with maleic anhydride under high temperature,and converted into maleated rosin acyl chloride 2.Then,fourteen novel maleated rosin-based disulfonamide compounds 4a-4n were synthesized through the AN-acylation reaction of compound 2 with A^-ary1 sulfonyl ethylenediamines 3a-3n prepared by ourself.And,substituted phenyl isothiocyanides 5a-5j were prepared by the reaction of substituted anilines with carbon disulfide,and converted into N-aryl thioureido ethylenediamines 6a-6j,followed by the N-acylation reaction of compound 2 with compounds 6a-6j to afford ten novel maleated rosin-based dithiourea compounds 7a-7j.The synthetic conditions were investigated preliminarily,and the target compounds were characterized by means of FT-IR,1H NMR,13C NMR,ESI-MS,and UV-vis.The fungicidal activity of the target compounds 4a-4n and 7a-7j against Fusarium oxysporum f.cucumerinum,Cercospora arachidicola,Physalospora piricola,Alternaria solani,and Gibberella Zeae was evaluated by agar well diffusion method.It was found that,at the concentration of 50 ?g/mL,compounds 4a-4n exhibited a certain inhibition activity against the five tested fungi,especially against Physalospora piricola,in which compound 4k(R=2-F)had inhibition rate of 66.8%against Physalospora piricola.Compounds 7a-7j exhibited a certain inhibition activity against the above-mentioned fungi,in which most of the compounds had inhibition rates of more than 60%,and compound 7i(R=4-Cl)had inhibition rate of 71.4%(B-class activity level).Besides,compound 7c(R=3-CH3)displayed inhibition rates of 62.9%and 66.8%against Cercospora arachidicola and Physalospora piricola,respectively.The herbicidal activity of compounds 4a-4n and 7a-7j was evaluated by rape petri dish and barnyard grass beaker method.It was found that,at the concentration of 100 ?gg/mL,only part of the compounds 4a-4n displayed weak growth inhibition activity against root of rape(Brassica campestris),and these compounds exhibited almost no growth inhibition activity agaist barnyard grass(Echinochloa crusgalli(L.)).Most of the compounds 7a-7j displayed weak growth inhibition activity against barnyard grass(Echinochloa crusgalli(L.),and these eompounds exhibited almost no growth inhibition activity agaist root of rape(Brassica campestris).