Synthesis And Biological Activity Of ?-pinene-based Phenyl Thiadiazole And Benzene Sulfonamide Compounds

Turpentine is a natural and preponderant resource of China,and its main component is ?-pinene.?-Pinene and its derivatives show a wide range of bioactivites.Various bioactive derivatives can be synthesized by structural modification of the molecule of ?-pinene.In this thesis,?-pinene was converted into N-carboxymethyl-terpinene-maleimide at first.Then,two types of novel?-pinene-based phenyl thiadiazoles and ?-pinene-based benzene sulfonamides with multi-functional groups and potential biological activity,were synthesized by chemical modification of carboxyl group in N-carboxymethyl-terpinene-maleimide,and by introduction of active thiadiazole and sulfonamide groups into the skeleton of N-carboxymethyl-terpinene-maleimide.This research aims at providing a new pathway for the deep development and utilization of turpentine.In this thesis,?-terpinene-maleic anhydride 3 was prepared by Diel-Alder cycloaddition reaction of maleic anhydride with a-terpinene converted from?-pinene under catalysis of protonic acid,followed by the reaction of 3 with glycine to obtain N-carboxymethyl-terpinene-maleimide 4.Then,nine novel a-pinene-based phenyl-thiadiazoles 7a-7i were synthesized by the reaction of acyl chloride of 4 with various substituted phenyl thiadiazoles.Besides,nine novel ?-pinene-based benzene sulfonamides 9a-9i were synthesized by the N-acylation reaction of acyl chloride of 4 with various N-aryl sulfonyl ethylenediamine.The synthetic conditions were investigated preliminarily.The target compounds were characterized by means of FT-IR,1H NMR,13C NMR,and ESI-MS technigues.The fungicidal activity of all the target compounds,a-pinene-based phenyl-thiadiazole 7a?7i and a-pinene-based benzene sulfonamides 9a?9i,and the intermediate 4 against Fusarium oxysporum f,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-1,compound 7d(R=3-Cl)exhibited inhibition rate of 92.6%(A-class activity level)against Physalospora piricola,and compound 7a(R=H)showed inhibition rate of 91.8%(A-class activity level)against Cercopora rachidicola.Compounds 9d(R=4-Cl)and 9h(R=2-NO2)had inhibition rate of 83.9%and 79.6%(B-class activity level)against Physalospora piricola,respectively,and compounds 9b(R=3-CH3)and 9i(R=3-NO2)had inhibition rate of 82.2%and 71.1%(B-class activity level)against Alternaria solani,respectively.Compounds 7d(R=3-Cl)and 7a(R=H)are lead compounds worthy of deep research.The herbicidal activity of all the target compounds,7a-7i and 9a-9i,and the intermediate 4 was tested by rape petri dish method and barnyard grass beaker method.It was found that,at the concentration of 100 ?g·mL-1,the target compounds 7 only displayed very weak herbicidal activity.Compound 9h(2-NO2)showed growth inhibition activity of 60.2%(B-class activity level)against root of rape(Brassica campestris).