Structural Diversity Derivatization And Application Based On Aminonitroguanidine(ANG)

More and more compounds containing multi-nitrogen atoms were developed as excellent pesticides in past twenty years. This trend makes them being payed more attention in agro-chemicals field.3-Amino-1-nitroguanidine(ANG) was first synthesized by Phillips in 1920s. As a compound with high nitrogen content of 58.81%, ANG and its derivatives have been gradually attracted much attention in energetic material field. Although ANG is a compound containing multiple active functional groups, little is concerned and studied about the diversity of its chemical reaction. Hence, more studies and applications in the field of organic synthesis and biological activity compounds were needed to be explored. In past works in our lab, several series of ANG derivatives had been designed and synthesized, many of them showed excellent insecticidal or fungicidal activity. This reveals the immense potential of ANG in novel pesticides development. On the basis of our previous work, five new class of ANG derivatives were designed and synthesized in this paper, the structures of them were comfirmed by 1H NMR,13C NMR, HRMS or elemental analysis. Their bioactivities were evaluated in vitro or in vivo, and their qualitative or quantitative structure-activity relationship (QSAR) were also discussed.More detaied conclusions could be illustrated as follows:1. Total 50 compounds numbered as ZNQ-16001-ZNQ-16050 in series I were synthesized and evaluated for fungicidal activity in vitro at the concentration of 50μg/mL. The results showed that R1 played a crucial role for their fungicidal activity. When R| was 4-chlorophenyl (ZNQ-16025 ～NQ-16028), their fungicidal activities against six tested pathogens, sclerotinia sclerotirum, pythium aphanidermatum, phyricularia grisea, rhizoctonia solani, Fusarium oxysporum f. sp. vasinfectum (Atk.) Snyder & Hansen were usually higher than other target compounds and compound ZNQ-16027 exhibited highest inhibition rate (70.4%) against sclerotinia sclerotirum that was equivalent to Chlorothalonil (71.6%). There was little effection for their fungicidal activities when free amines were salted, such as compounds ZNQ-16047-ZNQ-16050 displayed.2. Total 31 compounds numbered as ZNQ-16052-ZNQ-16083 in series Ⅱ were synthesized. The insectidical activities of the target compounds against Myzus persicae Sulzer was screened. At the concentration of 500 μg/mL, most of compounds Ⅱ showed good insectidical acivities and corrected mortalities were above 90%. The results of precision insecticidal activity of selected compounds against Myzus perscicae Sulze showed that compounds ZNQ-16052 and ZNQ-16053, which R2 was 2-chloropyridine-5-methylene, were obviously higher than others. The LC50 of compound ZNQ-16053 was 9.5μg/mL, suggesting that it was valuable for further development. The fungicidal activities in vitro of compounds 11 was also evaluated at 50 μg/mL. Generally. these compounds showed poor fungicidal activities against six tested pathogens, only ZNQ-16070 gave 74.7% inhibition against Ahernaria mali.3. Twenty five compounds numbered as ZNQ-16084-ZNQ-16108 in series III were synthesized. Their preliminary insectidical activities against Myzus persicae Sulzer was screened at the concentration of 500 μg/mL and the results showed that they were excellent insectides against Myzus persicae Sulzer. At 500 μg/mL, the corrected mortalities of most compounds Ⅲ were above 85% and ZNQ-16084, ZNQ-16085, ZNQ-16096 were even more than 95%. The precision insecticidal activities of selected compounds against Myzus perscicae Sulze showed the LC50 of compound ZNQ-16085, ZNQ-16087, ZNQ-16094. ZNQ-16096 was 9.5,8.1,10.0.9.9 μg/mL respectively.4. Total 53 compounds numbered as ZNQ-16109-ZNQ-16163 in series IV and V were synthesized. Their fungicidal activities were evaluated in vitro at 50 μg/mL against nine pathogens. Generally, all of compounds exhibited good fungicidal activities and broad fungicidal spectrum. Most of them showed excellent fungicidal activities against sclerotinia sclerotirum. The inhibition rate of compounds ZNQ-16118, ZNQ-161142, ZNQ-16143. ZNQ-16146. ZNQ-16147, ZNQ-16153, ZNQ-16158. ZNQ-16159 against sclerotinia sclerotirum reached to 93.7%,91.6%, 94.1%,92.4%,90.3%,91.2%,90.1%,98.3%respectively. The precision fungicidal activity of selected compounds against sclerotinia sclerotirum showed the EC50 of compound ZNQ-16142, ZNQ-161143. ZNQ-16146, ZNQ-16152. ZNQ-16153, ZNQ-16154. ZNQ-16156. ZNQ-16157 was 4.08.3.90,4.40.3.91,4.07,4.60.3.90,3.51μg/mL respectively, the activity of IV was obviously more effective than compound V. The in vivo fungicidal activities of some target compounds were evaluated using living spraying method (wheat powdery mildew, cucumber downy mildew, corn rust and cucumber anthracnose) and spore germination method (rice blast and cucumber mould). At the concentration of 400 μg/mL, most compounds showed 100% inhibition in living spraying assay. At 25 μg/mL, the inhibition rate of compound ZNQ-16109 was 88% and 80% respectively against wheat powdery mildew and corn rust, equivalent to Kresoxim-methyl. Most of elected compounds gave 100% spore germination control against rice blast at 25 μg/mL, but they were completely ineffective to cucumber mould.