The Synthesis And Biological Activity Of3,3-dimethyl-1-(1,2,4-triazol-1-yl) Butan-2-one Oxime Ether Acylamides

Oxime compounds have excellent insecticidal, herbicidal, fungicidal and plant growthregulation activities. In addition,1,2,4-triazoles possess the following merits as antiseptics:high efficiency, broad-spectrum, low toxicity, resistance, and double-effectiveness. Besides,as plant growth regulators, such compounds are also of the following features, high yield,early maturity, lodging resistance and stress tolerance. Due to the outstanding biologicalactivities of the acylamides, such as sterilization, acaricidal, insecticidal and herbicidal, theacylamide structure is often chosen as the effective group in the work of new pesticide design.In order to search new compounds with higher activities and lower toxicity, a serials of3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one oxime derivatives were designed on the basisof association principle.In this study, we selected1-chloro-3,3-dimethylbutan-2-one and aromatic acetamides asraw materials, the former of which reacted with1,2,4-triazole to get3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one, then substituted C=N for the strong absorption electricalC=O group. Seventeen oxime ether acylamides were synthesized by Willianmsonetherification of acetamides and3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one oxime. Phasetransfer catalysts were used in both the acylation and etherification systems, which canreduced the side effects. Compared to the references, synthetic routes in this thesis weresimple and higher efficient.There may exist two configurations in the title compounds due to the presence of C＝Ndouble bond. Crystal of compound4f was obtained by directly ethanol recrystallizationmethod. This crystal was demonstrated to exhibit Z configuration through single crystal X-raydiffraction analysis, with obvious intra-molecular hydrogen bond between the proton of NHbond in molecular and2-bit nitrogen atom in triazole ring. There is aR11(10)ring system dueto the existence of intramolecular hydrogen bond. On the other hand, prevalence of π-πstacking effects between the adjacent triazole rings and Van der Waals force further stabilize thecrystal structure of molecular4f.Firstly, the samples4a~4q were tested in Ultra High Throughput in Vivo Screening(UHTVS) for their pesticidal activities. Then, Potter-spraying and leaf-dipping methods wereused to measure the insecticidal activity of tested compounds against M. separate, A. fabaeand T. urticae. No insecticidal compound was found. In addition, fungicidal activities of thetitle compounds against Rhizoctonia solani, Botrytis cinerea, Sclerotonia sclerotiorum,Gibberella zeae, Phytophythora capsici, Alternaria alternate and Blumeria graminis were evaluated using the mycelium growth rate test, a serials of oxime ether acylamides werediscovered to have promising bactericidal and herbicidal activities.The inhibition rates ofcompounds4n and4o against Sclerotonia sclerotiorum were71.0%and52.3%at theconcentration of25mg/L, respectively. Methods of postemergence processing and soiltreatment against Abutilon theophrasti, Amaranthus spinosus L, Chenopodium album,Digitaria sanguinalis, EchinNOCHloa crus-galli and Setaria viridis at2250g ai/ha were usedto evaluate the herbicidal activity of titile compounds. The final results illustrated thatcompound4b,4c,4,4j and4k showed excellent herbicidal activities at different degrees.Through postemergence processing method, herbicidal activities of compound4b againstAbutilon theophrasti, Amaranthus spinosus L and Chenopodium album were70%,90%and80%, respectively. And those of compounds4c and4j against Amaranthus spinosus L andChenopodium album were both60%and70%respectively, all of which of compounds4c and4j were70%. It was noticible that with the method of soil treatment to Amaranthus spinosus Land Chenopodium album, only compound4b showed certain heibicidal activities, both ofwhich were90%.