Synthesis And Biological Activity Of Novel Dehydroabietic Acid-based Sulfamide And Thiourea Compounds

Rosin is a natural,renewable and preponderant resource of China,and disproportionated rosin is one of the main modified products of rosin.As the most abundant component of disproportionated rosin,dehydroabietic acid is a diterpene resin acid which has phenanthrene skeleton,carboxyl group and several chiral centres.Dehydroabietic acid and its derivatives show a variety of bioactivities.In recent years,it has become one of the research focuses for synthetic organic chemistry to synthesize bioactive compounds through structural modification of dehydroabietic acid.In this thesis,two types of novel dehydroabietic acid-based compounds with potential biological activity were synthesized by introduction of active sulfonamide and thiourea groups into the skeleton of dehydroabietic acid using dehydroabietic acid as starting material.This research aims at providing a new pathway for the deep processing of dehydroabietic acid.In this thesis,dehydroabietic acid acyl chloride 2 was prepared by the reaction of dehydroabietic acid with thionyl chloride,and N-aryl sulfonyl ethylenediamine 4 was prepared by the reaction of aryl sulfonyl chloride with ethylenediamine.Then,twelve novel dehydroabietic acid-based sulfonamide compounds 5a-51 were synthesized by the N-acylation reaction of 2 with 4 in the presence of DMAP as catalyst.Intermediates 7 were prepared by the reaction of aryl isothiocyanates with ethylenediamine.Then,ten novel dehydroabietic acid-based thiourea compounds 8a?8j were synthesized by the reaction of 2 with 7 under catalysis of DMAP.All the target compounds were analyzed and characterized by means of FT-IR,1H-NMR,13C-NMR,and ESI-MS.The fungicidal activity of the target compounds 5 and 7 against Fusarium oxysporum f.sp.Cucumerinum,Physalospora piricola,Alternaria solani,Cercospora Rachidicola,and Fusarium graminearum was evaluated by the agar well diffusion method.It was found that,at the concentration of 50?g·ML-1,both compounds 5 and compounds 7 exhibited a certain inhibition activity against the five tested fungi,especially against Physalospora piricola,in which compound 5f(R=3-Br)and compound 7b(R=2-Me)had inhibition rates of 68.3%and 64.2%,respectively,against Physalospora piricola.Compound 5c(R=3-Me)showed the best inhibition rates of 73.6%and 65.6%against Alternaria solani and Cercospora Rachidicola,respectively.The herbicidal activity of the title compounds 5 and 7 was evaluated by rape petri dish method and barnyard grass beaker method.The preliminary test result showed that,at the concentration of 100 ?g/mL,most of the title compounds exhibited a certain growth inhibition activity against rape root(Brassica campestris),in which compound 5d(R=4-OMe)had inhibition rate of 57.1%.The two types of compounds only displayed weak growth inhibition activity against barnyard grass(Echinochloa crusgalli(L.)).