Synthesis And Biological Activity Of N-aminoethyl-terpinene-maleimide-based Thiourea And Amide Compounds

Turpentine is a natural and preponderant resource of China(especially in Guangxi),and its main component is ?-pinene.?-Pinene and its derivatives show various biological activities.In recent years,it has become one of the research focuses for forest chemistry and synthetic organic chemistry to synthesize bioactive compounds through structural modification of ?-pinene.In this thesis,?-pinene was converted into N-aminoethyl-terpinene-maleimide at first.Then,two types of novel N-aminoethyl-terpinene-maleimide-based derivatives with multi-functional groups and potential biological activity,N-aminoethyl-terpinene-maleimide-based thioureas and N-aminoethyl-terpin-ene-maleimide-based amides,were designed and synthesized by chemical modification of amino group in N-aminoethyl-terpinene-maleimide,and by introduction of active thiourea and amide groups into the skeleton of N-aminoethyl-terpinene-maleimide.This research aims at providing a new way for deep exploitation and high-value utilization of turpentine.In this thesis,?-pinene was converted into a-terpinene by rearrangement under catalysis of protonic acid.?-Terpinene-maleic anhydride adduct 3 was prepared by Diels-Alder cycloaddtion reaction of ?-terpinene with maleic anhydride.Then,N-aminoethyl-terpinene-maleimide 4 was prepared by the reaction of 3 with ethylenediamine.Ten novel N-aminoethyl-terpinene-maleimide-based thioureas 5a-5j were synthesized by the reaction of 4 with substituted phenyl isothiocyanates.Eleven novel N-aminoethyl-terpinene-maleimide-based amides 6a-6k were synthesized by the N-acylation reaction of the intermediate 4 with substituted benzoyl chlorides under catalysis of triethylamine.The synthetic conditions of the target compounds 6 were investigated preliminarily.The target compounds were analyzed and characterized by means of 1H NMR,13C NMR,FT-IR,ESI-MS and UV-vis.The fungicidal activity of the intermediate 4,all the target compounds N-aminoethyl-terpinene-maleimide-based thioureas 5a-5j and N-aminoethyl-terpinene-maleimide-based amides 6a-6k against Fusarium oxysporum f,Cercospora arachidicola,Physalospora piricola,Alternaria solani and Fusarium graminearum was evaluated by in vitro method.It was found that,at the concentration of 50 ?g·mL-1,the target compounds 5a?5j exhibited a certain activity against all of the tested fungi,in which compound 5h(R=2-CH3O)had the best inhibition rate of 64.2070 against Alternaria solani.The target compounds 6a?6k showed a eertain inhibition activity against all of the tested fungi,especially aga:inst Physalospora piricola,in which compound 6g(R=3-CH3)had inhibition rate of 63.6%.The intermediate 4 only displayed weak inhibition activity against all of the tested fungiThe herbicidal activity of the intermediate 4 and all the target compounds 5a?5j and 6a?6k was tested by rape petri dish method and barnyard grass beaker method.It was found that,the intermediate 4 exhibited excellent growth inhibition activity of 92.3%(A-class activity level)against rape root(Brassica campestris)at the concentration of 100?g·mL-1.A few of compounds 5 showed a certain growth inhibition activity against rape root,in which compound 5h(R=2-CH3O)had the best inhibition rate of 82.0%(A-class activity level).A few of compounds 6 displayed a certain growth inhibition activity against rape root,in which compound 6g(R=3-CH3)had the best inhibition rate of 71.5%(B-class activity level).All the target compounds 5 and 6 only displayed weak growth inhibition activity against barnyard grass(Echinochloa crusgalli(L.)).