含三氟甲基吡啶酰胺结构的N-氰基磺酰亚胺衍生物的合成及生物活性

Synthesis and Biological Activity of N-Cyano Sulfonimide Derivatives Bearing Trifluoromethyl Pyridinamide

采用活性亚结构拼接法,设计合成了系列新型含三氟甲基吡啶酰胺结构的N-氰基磺酰亚胺类衍生物,其结构经1H NMR、13C NMR、19F NMR和HRMS进行了表征.评估了它们对柑橘溃疡病菌(Xanthomonas axonopodis pv.citri)、烟草青枯病菌(Ralstonia solanacearum)和水稻白叶枯病菌(Xanthomonas oryzae pv.oryzae)的杀菌活性及对小菜蛾(Plutella xylostella)的杀虫活性.结果表明,部分化合物表现出了良好的抗菌活性和中等的杀虫活性.其中,在200 mg/L质量浓度下,3-氯-(2-(N-氰基-S-(3,4-二氟苄基)磺酰亚胺酰基)乙基)-5-(三氟甲基)吡啶酰胺(G10)对柑橘溃疡病菌、烟草青枯病菌和水稻白叶枯病菌的抑制率分别为67%、53%和48%,3-氯-(2-(N-氰基-S-(2,5-二氟苄基)磺酰亚胺酰基)乙基)-5-(三氟甲基)吡啶酰胺(G17)对柑橘溃疡病菌的抗菌活性为69%,(2-(S-(2-溴-4-氟苄基)-N-氰基磺酰亚胺基)乙基)-3-氯-5-(三氟甲基)吡啶酰胺(G14)对水稻白叶枯病菌的抑制率为49%.在100 mg/L时,(2-(S-(4-溴-2-氟苄基)-N-氰基磺酰亚胺基)乙基)-3-氯-5-(三氟甲基)吡啶酰胺(G1)、3-氯-(2-(N-氰基-S-(3-氟苄基)磺酰亚胺基)乙基)-5-(三氟甲基)吡啶酰胺(G7)、3-氯-(2-(N-氰基-S-(2,4-二氟苄基)磺酰亚胺酰基)乙基)-5-(三氟甲基)吡啶酰胺(G8)和G10也有中等的杀菌活性,在测试浓度下,部分化合物的活性略高于对照药剂或与之相当.此外,在500 mg/L时,化合物G10和3-氯-(2-(N-氰基S-(4-异丙基苄基)磺酰亚胺基)乙基)-5-(三氟甲基)吡啶酰胺(G11)对小菜蛾的致死率分别为77%和70%.

A series of novel N-cyano sulfonyimide derivatives containing trifluoromethyl pyridinamide were designed and synthesized by combination method of active substructure,and their structures were identified by 1H NMR,13C NMR,19F NMR and HRMS.Their antibacterial activity against Xanthomonas axonopodis pv.citri(Xac),Ralstonia solanacearum(R solanacearum),Xanthomonas oryzae pv.oryzae(Xoo)and insecticidal activity on Plutella xylostella(P.xylostella)were investigated.Some of the compounds were tested to display good antibacterial and moderate insecticidal activities.Among them,3-chloro-N-(2-(N-cyano-S-(3,4-difluorobenzyl)sulfonimidoyl)ethyl)-5-(trifluoromethyl)picolinamide(G10)showed 67%,53%and 48%activities against Xac,R.Solanacearum and Xoo at 200 mg/L,respectively.The antibacterial activity of 3-chloro-N-(2-(N-cyano-S-(2,5-difluorobenzyl)sulfonimidoyl)ethyl)-5-(trifluoromethyl)picolinamide(G17)against Xac was 69%and the inhibition rate of N-(2-(S-(2-bromo-4-fluorobenzyl)-N-cyanosulfonimidoyl)ethyl)-3-chloro-5-(trifluoromethyl)picolinamide(G14)on Xoo was 49%.N-(2-(S-(4-Bromo-2-fluorobenzyl)-N-cyanosulfonimidoyl)ethyl)-3-chloro-5-(trifluoromethyl)picolinamide(G1),3-chloro-N-(2-(N-cyano-S-(3-fluorobenzyl)sulfonimidoyl)ethyl)-5-(trifluoromethyl)picolinamide(G7),3-chloroN-(2-(N-cyano-S-(2,4-difluorobenzyl)sulfonimidoyl)ethyl)-5-(trifluoromethyl)picolinamide(G8)and G10 also had moderate bactericidal activity at 100 mg/L,which are slightly higher than or comparable to that of the positive controls at the corresponding concentration.Moreover,compounds G10 and 3-chloro-N-(2-(N-cyano-S-(4-isopropylbenzyl)sulfonimidoyl)ethyl)-5-(trifluoromethyl)picolinamide(G11)also showed moderate insecticidal activity against P.xvlostella of 77%and 70%at 500 mg/L.