Synthesis And Bioactivity Of Novel Triazolinones And Tetrazolinones Derivatives

Triazolinone and tetrazolinone derivatives have been found to have widespread biological activities, especially as herbicides, which show characteristics of high bioactivities, low poison, and environmental friendship. In the contemporary herbicides research area, they become one of the most popular topics. In order to search for novel triazolinone and tetrazolinone derivatives with high activities, according to the bioisosterism and the connecting principle of actively biological groups, thirteen series and two kinds of two hundred and fifty-two triazolinone and tetrazolinone derivatives were designed and synthesized in good to excellent yields. Their bioactivities, structure-activity relationship and spectral properties were studied, and many of them were found to show excellent herbicidal activities. Meanwhile, tetrazolinone skeleton was found to display good insecticidal activities. This dissertation may be summarized as follows:The application, synthesis, reaction characteristics and metabolisms of Triazolinone and tetrazolinone derivatives were summarized, and the structure-activity relationship was given.One-hundred-sixty-six triazolinone derivatives, including 1-{2-[2-alkylthio(sulfinyl or sulfonyl)]-6-substitutedbenzo[d]thiozol-5-yl}-3-methyl-4-substituted-1H-1,2,4-triazol-5(4H)-on e 2-7, 2-8, 1-[2,4-disubstituted-5-(isoindoline-1,3-dione)phenyl-2-yl]-3-methyl-4-substituted-1H-1,2,4-triazol-5(4H)-one 2-9, 1-{2,4-disubstituted-5-[3-(4-substitutedphenyl)urea]phenyl-1-yl}-3-methyl-4-substituted-1H-1,2,4-triazol-5(4H)-one 2-10, and 1-(2,4,5-trisubstituted phenyl)-3-methyl-4-substituted-1H-1,2,4-triazol-5(4H)-one 2-13, 2-14, 2-15, 2-16, were designed and synthesized by a multiple step synthetic procedures. Their structures were characterized by ¹H NMR, GC-MS spectroscopies, element quantitative analysis and X-Ray analysis. The results of herbicidal activities indicated that many compounds displayed excellent herbicidal activity against tested weed at the dosage of 150 g/hm², such as 2-7mm, 2-7nn, 2-7oo, 2-7pp, 2-7qq, 2-7tt,2-7ww,2-7hhh,2-7iii,2-7jjj,2-7kkk, 2-9d, 2-13c. Those were the same as commercial herbicide Sulfentrazone. These compounds, such as 2-7rr,2-7ss,2-7fff,2-7ggg, were more excellent against Dicotyledoneae than Monocotyledoneae weeds, The compounds 2-15e, 2-16d showed 100% herbicidal activity against Amaranthus retroflexus and Chenopodium album at the dosage of 450 g/hm². The secure appraisal indicated that compound 2-7qq was safe to paddy rice, cotton, corn, compound 2-13c to paddy rice under 150 g/hm² dosage; Under 450 g/hm² dosage, compound 2-15e was safe to cotton, soybean and rape, compound 2-16d to paddy rice, cotton, soybean and rape.Eighty six tetrazolinone derivatives bearing structurally diverse substituents on 4-position, 1-aryl-4-substituted-1,4-dihydro-5H-tetrazol-5-ones 3-3, 1-[(5-alkylthio-4-phenyl-4H-1,2,4-triazol-3-yl)methyl]-4-(4-chlorophenyl)-1,4-dihydro-5H-tetrazol-5-one 3-7,1 -(2-alkylthio-1,3,4-oxadiazole-5-yl)-methylene-4-(4-chlorophenyl)-1H-tetrazol-5(4H)-ones 3-9, 1-(2-alkylthio-1,3,4-thiadiazole-5-yl)-methylene-4-(4-chlorophenyl)-1H-tetrazol-5(4H)-ones 3-11, and 1-[2-(3-alkyloxyimino)-propyl]-4-(4-chlorophenyl)-1,4-dihydro-tetrazol-5-one 3-15 were designed and synthesized in good yields by a multiple step synthetic procedures. Their structures were characterized by ¹H NMR, ¹³C NMR, GC-MS spectroscopies, element quantitative analysis and X-Ray analysis. The results of test indicated that all the target compounds did not displayed good herbicidal activity, however, some of them exhibited excellent in vivo insecticidal activity against Tetranychus cinnabarnus, Mythima separate, Aphis medicagini at the concentration of 250 mg/L and 500 mg/L, such as 3-3a, 3-3b, 3-3e, 3-3o, 3-7k, 3-3c, 3-9a, 3-11b, 3-11g. To our knowledge, this is the first report about the insecticidal activity of tetrazolinone derivatives, which indicated that the tetrazolinone scaffold could be identified as a novel insecticidal lead structure.