Design,Synthesis And Bioactivity Of Pesticide Molecules Related To Carbohydrates And Oleanolic Acid

This paper is mainly about novel pesticide discovery with carbohydrates and terpenes(Oleanolic acid)as subjects based on natural products,which possess excellent bioactivities,good environment compatibility and diversity of type and structure.It consists of two parts:Synthetic studies of natural oligosaccharides related to certain pesticide activities;Design,synthesis and bioactivity investigation of glucosamine-6-phosphate synthase(Glms)inhibitors.Part ?:Total synthesis of oligosaccharides in nitrogen fixing spirillum with certain pesticide activities.Total synthesis of two isomeric tetrasaccharides(1,2),the repeating units from the lipopolisaccharides of the nitrogen fixing bacterium Azospirillum brasilense S17 and Azospirillum lipoferum SR65 was achieved via commercially available L-rhamnose,D-glucose as the starting materials.The structures of the target compounds and intermediates were characterized by 1H NMR?13C NMR?HSQC?HRMS or elemental analysis.Part ?:Design,synthesis and bioactivity investigation of glucosamine-6-phosphate synthase(Glms)inhibitors.1.Eight 3-amino-3-deoxy-D-glucose derivatives(3),two D-glucosamine-6-phosphate analogs(4)and one 2-amino-2-deoxy-D-mannose derivatives(5)were designed and synthesized from commercially available D-glucose.The structures of the target compounds were characterized by 1H NMR,and some of them were characterized by 13C NMR,MS and 31P NMR.Preliminary studies based on means of the Elson-Morgan method indicated that some compounds exhibited some inhibitory activity of glucosamine-6-phosphate synthase(G1mS)at the concentration of 0.35 mM,but the original fungicidal activities results showed that the compounds exhibited poor fungicidal activities at the concentration of 50 ?g/mL.2.In order to develop potential glucosamine-6-phosphate synthase inhibitors and anti-fungal agents,twenty five oleanolic acid oxime esters(6)and fourty five oleanolic acid oxime ethers(7)were designed and synthesized in an efficient way.The structures of the new compounds were confirmed by MS,HRMS,1H-NMR and 13C-NMR.Preliminary studies based on means of the Elson-Morgan method indicated that many compounds exhibited some inhibitory activity of glucosamine-6-phosphate synthase(GlmS),and the original fungicidal activities results showed that some of the compounds exhibited good fungicidal activities to Sclerotinia scleiotirum(Lib.)de Bary,Rhizoctonia solani Kuhn and Botrytis cinerea Pers at the concentration of 50 ?g/mL.3.Seven oleanolic acid glycoconjugates(5)were designed and synthesized using oleanolic acid and monosaccharides as starting materials.the new compounds were confirmed by HRMS,1H-NMR and 13C-NMR.Preliminary studies based on means of mycelium growth rate,indicated that all the compounds possess certain fungicidal activity against Sclerotinia sclerotiorum(Lib.)de Bary,Rhizoctonia solani Kuhn,Botrytis cinerea Pers and Phytophthora parasitica Dast.4.Two fructose-6-phosphate analogues(9)were designed and synthesized using D-arabinose as starting materials.The new compounds were confirmed by 1HNMR?13C NMR?31P NMR?19F NMR,HRMS and HPLC.Preliminary studies based on means of IC50 in three ways:Elson-morgen,GluPA and Isomerases,indicated that all the compounds possess certain inhibitory activity of glucosamine-6-phosphate synthase(GlmS),and it give support to the mechanism for the binding and consecutive opening of the cyclic sugar compared the relationship between structure and activity.