| Pesticides play an important role in protecting human life,food production and environmental protection and other fields from insect invasion.With the development of agriculture,high toxicity of the old varieties are not adapted to the needs of modern and gradually eliminated.To quickly meet the market demand for efficient and low toxicity of pesticides,we need to establish efficient pesticide product creation mechanism.Our group proposed a new pesticide creation technology-the Plug-in Molecular Theory,to meet the requirements of rapid creation and dramastically reduced the time.In the preliminary work of our group,we devoted to the synthesis of the small plug-in molecules,and have designed and synthesized several kinds of intermediates which are novel and powerful and easy to be stitched with other pharmacophores.In this paper,based on the preliminary research,the plug-in molecular alkoxylamine was designed and synthesized by using the molecular plug-in molecular theory.A total of 116 new NO derivatives from 4 series of Ⅰ-Ⅳ were synthesized by using the plug-in molecular theory.(As shown in the following figure)These compounds were confirmed by 1H NMR,13C NMR,high-resolution mass spectroscopy and X-ray crystal structure.The relationship between its biological activity and structure was also investigated.1.A total of 39 derivatives from series I were synthesized.series la was from ZNQ-17001-ZNQ-17034 and series Ib was from ZNQ-17035-ZNQ-17039.The insecticidal activity of target compounds was tested against Myzus perscicae(Sulzer).At the concentration 50 μg/mL,several compounds showed good insecticidal activity against Myzus persicae and the lethal rate was higher than 70%.The result of precision insecticidal activity showed that when the R2 group was 2-chlorothiazole-5-methylene(ZNQ-17007,ZNQ-17008),the activity was higher than that of R2 for other aryl groups.The LC50 value of ZNQ-17007 to Myzus persicae was 0.38 μg/mL,which was better than the other compounds.The LC50 value was inferior to imidacloprid,but still potential for further research or developed as a lead compound.Furthermore,the EC5o value of ZNQ-17007 to honey bee was 5.56 μg/mL,which was comparable to Guadipyr.The property of low toxicity indicated that the toxicity of neonicotinoid insecticides to bees can be solved by structural modification.The(Ib)(ZNQ-17035 to ZNQ-17039)series were tested fungicidal activity at a concentration of 50 μg/mL.In general,these compounds showed poor fungicidal activity,the inhibit rate was lower than 50%against eight fungi,but the insecticidal activity of these compounds is good,LC50 value of compound ZNQ-17035 was1.5 μg/mL against Myzus persicae.2.Series Ⅱ of twenty compounds were synthesized.The in vitro fungicidal activity of the target compound Ⅱ at the concentration 50 μg/mL was tested against seven fungi by using azoxystrobin and trifloxystrobin as control agents.Compounds ZNQ-17040 and ZNQ-17059 showed some fungicidal activity,and the compound ZNQ-17059 was more prominent,the inhibit rate was higer than 40%again four fungi,but still not as good as commercial agents azoxystrobin and trifloxystrobin.The insecticidal activity of target compounds was tested against Aphis gossypii(Glover).Compounds ZNQ-17040 and ZNQ-17057 showed excellent insecticidal activity and the lethal rate higher than 70%.3.Series Ⅲ of thirty-seven compounds were synthesized.The in vitro fungicidal activity of the target compound Ⅲ was tested against seven fungi.(1)The results showed that most of the target compounds showed excellent fungicidal activity agains Sclerotinia sclerotiorum,among these compounds which 17 compounds had more than 90%inhibition rate at the concentration 50 μg/mL.The EC50 values of all the target compounds were tested against Sclerotinia sclerotiorum,The EC50 value of ZNQ-17068 was 0.08 μg/mL,which was better than commercial agents.(2)Some of the target compounds showed a broad spectrum of fungicidal activity and showed moderate fungicidal activity against Rhizoctonia solani,Phytophthora infestans,Pyricularia grisea Botrytis cinerea,Pythium aphanidermatum.The inhibition rate of a variety of pathogens were better than the control,such as compounds ZNQ-17060,ZNQ-17065,ZNQ-17068,ZNQ-17088 and ZNQ-17089.Five compounds were selected to caculate he EC50 values against the other six pathogens.The EC50 value of ZNQ-17089 against Botrytis cinerea was 6.59 μg/mL,which was better than commercial agents.The EC50 value of ZNQ-17060、ZNQ-17068 and ZNQ-17088 against Phytophthora infestans were 21.49,12.60,17.29μg/mL,respectively,which was better than Trifloxystrobin.The EC50 value of ZNQ-17088 and ZNQ-17089 against Pythium aphanidermatum were 18.14,20.30 μg/mL,respectively,which were better than Azoxystrobin.The EC50 value of ZNQ-17060 and ZNQ-17068 against Pyricularia grisea were 8.42,6.86 μg/mL,respectively,which were comparable to the control.(3)The series compounds showed poor fungicidal activity against Colletotrichum orbiculare.4.Series IV of 20 compounds were synthesized and their fungicidal activity was evaluated.The in vitro fungicidal activity of compound IV against eight pathogens was determined at 50μg/mL.The results showed that all the target compounds showed a certain fungicidal activity,and the fungicidal activity against Setosphaeria turcica was excellent,The EC50 value of ZNQ-17102,ZNQ-17104 and ZNQ-17108 were 9.6,6.5,7.8 μg/mL,respectively,which was better than commercial agents. |
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