Synthesis And Biological Activity Of N-aminoethyl-terpinene-maleimide-based Sulfamide And Imidazole Compounds

Turpentine is a renewable,natural,and preponderant resource of China,and its main component is α-pinene.α-Pinene and its derivatives show extensive bioactivities.In recent years,it has become one of the research focuses for synthetic organic chemistry and chemistry of fine chemicals to synthesize bioactive compounds by structural modification of a-pinene.In this thesis,a-pinene was converted into a-terpinene-maleic anhydride adduct(TMA)at first,then,TMA was converted into N-aminoethyl-terpinene-maleimide(ATM).Two types of N-aminoethyl-terpinene-maleimide-based derivatives with multifun-ctional groups and potential bioactivity,N-aminoethyl-terpinene-maleimide-based sulfamides and N-aminoethyl-terpinene-maleimide-based imidazoles,were designed and synthesized by chemical modification of TMA and ATM,respectively.This research aims at providing a new pathway for the development and utilization of turpentine.In this thesis,a-pinene was converted into α-terpinene through Wagner-Meerwein rearrangement,followed by Diels-Alder cycloaddtion reaction of a-terpinene with maleic anhydride to obtain α-terpinene-maleic anhydride adduct(TMA).Then,twelve N-aminoethyl-terpinene-maleimide-based sulfamide compounds 5a-51 were synthesized by introduction of N-aryl sulfonyl ethylenediamine into the skeleton of TMA.N-Aminoethyl-terpinene-Maleimide(ATM)was prepared by the reaction of TMA with ethylenediamine,followed by the modification of the amino group in ATM to afford nine N-aminoethyl-terpinene-maleimide-based imidazole derivatives 7a～7i under catalysis of zinc oxide.The synthetic conditions were investingated preliminarily.The target compounds were analyzed and characterized by means of FT-IR,1HNMR,13C NMR,and ESI-MS techniques.The fungicidal activity of ATM and all the target compounds was evaluated against Cercospora arachidicola,Physalospora piricola,Fusarium oxysporum f.cucumerinum,Gibberella Zeae,and Alternaria solani.It was found that ATM exhibited weak fungicidal activity against the five tested fungi.The target compounds 5 and 7 exhibited a certain fungicidal activity against the above-mentioned fungi,especially against Physalospora piricola,in which compound 5c(R=3-CH3)and compound 7i(R=2-OCH3)had inhibition rates of 62.3%and 64.5%,respectively.Compound 5c(R=3-CH3)and compound 7i(R=2-OCH3)had the same inhibition rate of 68.8%against Cercospora arachidicola,and they had the inhibition rates of 68.3%and 64.2%against Alternaria solani,resoectively.The herbicidal activity of ATM and all the target compounds was evaluated by barnyard grass beaker method and rape petri method.Herbicidal assay showed that ATM exhibited excellent growth inhibition activity against root of rape with inhibiton rate of 92.3%(A activity level).Compounds 5 and 7 only showed weak inhibition activity against root of rape and barnyard grass.