含多氟烷基吡唑环的邻甲酰氨基苯甲酰胺类化合物的合成及杀虫活性

以2,3-二氯吡啶和水合肼为起始原料,经取代、缩合、氧化、醚化、成环和开环等多步反应合成一系列结构新颖的含多氟烷基吡唑环的邻甲酰氨基苯甲酰胺类化合物,结构经1H NMR和HRMS确证,并测试了目标化合物的杀虫活性.杀虫活性结果表明,在浓度0.8 mg/L下,大部分化合物对粘虫(Mythimna separata Walker)具有100%杀虫活性;在浓度2 mg/L下,N-(4-氯-2-(异丙基氨基甲酰)-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-((1-甲基-3-五氟乙基-4-三氟甲基-1H-吡唑-5-基)氧基)-1H-吡唑-5-酰胺(8c)和N-(4-氯-2-(环丙基氨基甲酰)-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-((1-甲基-3-五氟乙基-4-三氟甲基-1H-吡唑-5-基)氧基)-1H-吡唑-5-酰胺(8d)对斜纹夜蛾(Prodenia litura Fabricius)杀虫活性大于60%;在浓度0.08 mg/L下,N-(4-氯-2-(二甲基氨基甲酰)-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-((1-甲基-3-五氟乙基-4-三氟甲基-1H-吡唑-5-基)氧基)-1H-吡唑-5-酰胺(8l)对小菜蛾(Plutella xylostella Linnaeus)杀虫活性达到82.5%.     

N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺的合成及生物活性

通过改变传统氯虫酰胺中吡唑环上氨基甲酰基与吡啶环之间的相对位置, 或以其它芳环取代原分子中的吡啶环, 设计合成了24个结构新颖的N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺类化合物. 所有目标化合物的结构均通过¹H NMR谱、 元素分析或高分辨质谱表征确定. 初步的生物活性测试结果表明, 部分化合物对东方粘虫具有较好的杀虫活性, 其中化合物6m在浓度为50 mg/L时具有80%的杀虫活性. 同时, 在浓度为50 mg/L时目标化合物对5种常见病菌具有明显的抑制作用, 其中化合物6n和6x对苹果轮纹菌的抑菌率达62.1%.     

双酰胺类化合物的合成及生物活性研究

为了寻找高活性农药先导化合物,以甲霜灵为先导,通过活性基团拼接原理,设计合成了一系列未见文献报道的双酰胺类化合物,其结构经1H NMR、13C NMR和HRMS表征.初步的生物活性测试结果表明:在50 mg/L测试浓度下,化合物5j对黄瓜霜霉病显示出85%的抑制率;在500 mg/L剂量下,多数目标化合物对粘虫表现出较好的杀虫活性,其中化合物5b,5f,5g,5h,5i,5l对粘虫的致死率高达100%,在250 mg/L测试浓度下,化合物5f,5h,51对粘虫的致死率为50%.     

5-吡唑甲酰胺类衍生物的设计、 合成与生物活性

以2种5-吡唑甲酸为原料, 分别与噻唑胺和苯并呋喃胺发生缩合反应, 制备了23个新的5-吡唑甲酰胺类化合物; 采用核磁共振波谱和质谱等对目标化合物结构进行了表征; 对化合物B1和B3进行了量子化学计算、 前沿分子轨道及分子范德华表面静电势分析. 生物活性实验结果表明, 在500 mg/L浓度下部分化合物对黏虫和蚜虫有良好的杀虫活性, 其中化合物A1和B1对黏虫的致死率均为100%, 化合物B3, B4和C9对蚜虫的致死率分别为100%, 100%和95.54%; 在25 mg/L浓度下化合物A3对烟草赤星病菌的抑制率、 化合物C7对小麦赤霉病菌的抑制率以及化合物A1和A4对油菜菌核病菌的抑制率均大于50%.     

含噻唑环结构的新型吡唑酰胺类化合物的合成与杀虫活性研究

为了探索新的吡唑酰胺活性物质,基于吡螨胺的结构,将噻唑环通过酰胺键同吡唑环相连,合成了18个未见文献报道的吡唑酰胺类化合物,通过~1H NMR, ~(13)C NMR和元素分析等手段确证了其结构.生物活性测试研究显示,所有目标化合物在500μg/mL时对粘虫都有100%的杀虫活性. 7个目标化合物在500μg/mL时对蚜虫具有70%～100%的防治效果.同时, 3个目标化合物在500μg/mL时对朱砂叶螨显示出40%～50%的防效.     

含N-吡啶联吡唑杂环的(磺)酰胺类化合物的设计、合成及生物活性

以氯虫酰胺结构为基础, 设计合成了一系列含N-吡啶联吡唑杂环的酰胺及磺酰胺类化合物. 所有化合物的结构均通过元素分析和 ¹H NMR确证. 生物活性测试结果表明, 部分化合物对东方粘虫(4龄幼虫)和尖音库蚊(幼虫)表现出较好的杀灭活性. 化合物4a, 4k和5b在浓度为100 mg/L时对东方粘虫(4龄幼虫)的致死率均高于50%, 化合物4g 在浓度为2 mg/L时对尖音库蚊(幼虫)的致死率达100%.     

3-芳基异噁唑啉-吡唑-5-甲酰胺类化合物的合成及杀虫活性研究

以5,5-二甲氧基-2,4-二氧代戊酸乙酯为原料,设计合成了一系列含芳基异噁唑啉结构的吡唑-5-甲酰胺类化合物,产物结构经~1HNMR, ~(13)CNMR和HRMS确认.初步杀虫活性测试表明,多数化合物在500mg/L浓度下对粘虫(Mythimna separate)有着较高的活性(致死率≥80%),在100 mg/L的浓度下,有三种化合物对粘虫仍有中等程度的活性(致死率≥60%).在500 mg/L时,有四种化合物对苜蓿蚜(Aphis craccivora)也有较好的活性(致死率≥80%).因此,对该类化合物的结构优化可作为寻求新型杀虫剂而进行深入研究.     

含吡唑杂环二酰胺类化合物的合成与杀虫活性研究

通过活性亚结构拼接,合成16个含吡唑杂环的新型二酰胺类化合物,其结构通过了IR,1H NMR和HRMS的表征,其中目标化合物3h的结构经X单晶衍射进一步确认.初步生测结果表明在500 mg/L浓度下,部分化合物对粘虫和苜蓿蚜有致死活性;在100 mg/L浓度下部分化合物对茶尺蠖幼虫具有致死活性,其中毒症状表现为拒食.     

芳基吡唑氟尿嘧啶类化合物的设计、合成与杀虫活性研究

利用以γ-氨基丁酸(GABA)受体抑制剂芳基吡唑类杀虫剂的关键结构5-氨基-3-氰基-1-(取代苯基)吡唑为基本母核,设计、合成了26个创新结构芳基吡唑氟尿嘧啶化合物.目标化合物结构均采用1H NMR,FTIR和元素分析进行了结构确证,以小菜蛾和库蚊为靶标进行了杀虫活性测试.评价结果表明创制化合物具有优越的杀虫活性:在浓度为1000 mg·L-1时,化合物5a~5c,5e,5m及5u对库蚊具有100%的杀虫活性;在浓度为400 mg·L-1时,化合物5p对小菜蛾具有94.5%的杀虫活性.初步构效关系研究表明:苯环上取代基种类及位置等对化合物的生物活性有重要的影响.     

N-(取代噻唑-2-基)-菊酰胺类化合物的合成及生物活性研究

为了寻求新颖的氨基噻唑类先导化合物,以含各种取代基的2-氨基噻唑在其氨基位置与拟除虫菊酯类农药的活性基团——菊酸采用亚结构对接的方法合成了35个N-(取代噻唑-2-基)-菊酰胺类化合物,经1HNMR,ESI-MS和元素分析对化合物的结构进行了表征.初步生物活性测定表明,化合物3d,6a,6d,4a,4b,4c和4e在600mg/L下对小菜蛾具有100%的杀虫活性,化合物3d和7c在50mg/L下对多种常见病原菌具有显著的杀菌活性,全部化合物没有明显的除草活性.     

Synthesis and Insecticidal Evaluation of Novel Phthalic Diamides Containing 1,2,3‐Triazoles via Click Reaction

A series of novel phthalic diamide derivatives containing 1,2,3‐triazole moiety were synthesized using one‐pot click chemistry approach and characterized by ¹H NMR and HRMS. The insecticidal activity against armyworm (Mythimna separata), Tetranychu scinnabarinus and cowpea aphid (Aphis craccivora) was evaluated. Compounds 4II‐a and 4II‐i showed 50% insecticidal activity against armyworm (Mythimna separata) at the concentration of 4 mg/L and one‐third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.     

Synthesis and Biological Evaluation of Novel Anthranilic Diamides Containing N-H/CH3-1H-Pyrazole

In order to systematically study the structure-activity relationship of anthranilic diamides and develop insecticides with simple structure and high efficiency, a series of novel anthranilic diamides containing N-H/CH₃-1H-pyrazole was designed and synthesized. Their chemical structures were characterized by ¹H NMR spectra, high resolution mass spectrometry(HRMS) or ¹³C NMR spectra. The preliminary bioassay results indicated that all title compounds displayed moderate insecticidal activity against oriental armyworm(Mythimna separata) at 200 mg/L and fungicidal activities against six kinds of fungi at 50 mg/L, especially compound 5i showed 50% insecticidal activity at 25 mg/L. In addition, some compounds exhibited certain antitumor activities. It was demonstrated that the introduction of CH₃ group into pyrazole ring was superior to H for the insecticidal activity.     

三唑Schiff碱邻甲酰胺基苯甲酰胺衍生物的合成及生物活性

以2,4-二氯苯甲酸和2-氨基-3-甲基苯甲酸为起始原料,设计合成了8个新型含2,4-二氯苯基1,2,4-三唑Schiff碱邻甲酰胺基苯甲酰胺类化合物,通过1H NMR、IR及元素分析等技术手段对目标化合物进行了结构表征。 采用Airbrush喷雾法进行生物活性测试,结果表明,部分化合物具有不同程度的杀虫活性,其中化合物9a在600 mg/L浓度下对小菜蛾和粘虫的致死率均为100%。     

Synthesis,bioactivity, action mode and 3D-QSAR of novel anthranilic diamide derivatives

Several newly synthesized anthranilic diamide derivatives were found to exhibit excellent bioactivity. The action mode test and 3D-QSAR analysis provided valuable information for evaluation and future design of anthranilic diamide insecticides.     

Design,synthesis and biological activity of novel substituted pyrazole amide derivatives targeting Ec R/USP receptor

In order to discover highly active ecdysone analogs, a series of new substituted pyrazole amide derivatives were obtained using structure-guided optimization method and further screened for their insecticidal activities, in the basis of the core structures of the two active compounds N-(3-methoxyphenyl)-3-(tert-butyl)-1-phenyl-1H-pyrazole-5-carboxamide(6e) and N-(4-(tert-butyl)phenyl)-3-(tert-butyl)-1-phenyl-1H-pyrazole-5-carboxamide(6i), previously presented by us. The chemical structures of the title compounds were identified by spectral analyses. The preliminary bioassay results indicated that one among the synthesized pyrazole derivatives, compound 34, endowed with good activity against Mythimna Separata at 10 mg/L, which was equal to that displayed by the positive control tebufenozide. In addition, examples of molecular docking and molecular dynamics studies demonstrated that 34 may be the potential inhibitor to Ec R and its docking conformation was similar to that of tebufenozide. In addition, increasing the hydrophobic effect and considering the suitable bulk effect on pyrazole ring are beneficial to the inhibiting activity to Ec R and activity in vivo.     

Design,Synthesis, Biological Evaluation and SARs of Anthranilic Diamide Derivatives Containing Pyrrole Moieties

In order to find a new variety of ryanodine receptor(RyR) regulator with greater biological activity, a series of anthranilic diamide derivatives possessing pyrrole structure was designed and synthesized in this study. The pyrrole derivatives were evaluated for their insecticidal activity against Mythimna separata and Plutella xylostella. As indicated by the preliminary biological activities, compounds 12h-12j and 12l-12n exhibited a remarkable insecticidal activity against M. separata at 0.25 mg/L. Compared to control chlorantraniliprole, compound 12j exhibited more excellent insecticidal activity at 0.1 mg/L. Meanwhile, compounds 12c, 12h, 12i, 12j, 12l, and 12m were selected to test the insecticidal activity against P. xylostella, which led to the desirable insecticidal activity at 1×10^-3 mg/L. Notably, compound 12l demonstrated 47% insecticidal activity at 5×10^-6mg/L over the control. In addition, the biological mechanism of action of compound 12j was investigated by means of insect electrophysiology experiment.     

Synthesis,bioactivities and 3D-QSAR of novel avermectin B2a aglycon derivatives

Fourteen avermectin B2 a aglycon derivatives were designed and synthesized after removing the oleandrose disaccharide of avermectin B2 a.Their structures were characterized by’H NMR,13 C NMR,HMRS.Preliminary bioassays indicated that these compounds exhibited good insecticidal activity against diamondback moth at 200 mg/L,with mortality no less than 90%.Compounds 10 b,12 a,12 c,17 demonstrated good acaricidal activity against the adult mites,larvae,and good inhibition rate of hatching to mite eggs of Tetranychus cinnabarinus.Compounds 5,10 b,10 c exhibited excellent fungicidal activity against fourteen fungal pathogens in vitro.3 D-QSAR analysis showed that the fungicidal activity of avermectin B2 a aglycon derivatives would be increased when a negatively charged and bulky group was introduced at 13-position,which will be instructive for the further modification of avermectin B2 aaglycon.     

Design,synthesis and insecticidal activities of novel 1-substituted-5-(trifluoromethyl)-1H-pyrazole-4-carboxamide derivatives

A series of novel 5-(trifluoromethyl)-1H-pyrazole-4-carboxamide derivatives(6a–6n, 7a, 7b, and 8a-8f)were synthesised by placing the amide bond at the 4-position of the pyrazole ring. These derivatives differed from the structure of chlorantraniliprole analogues with the amide bond at the 5-position of the pyrazole ring. Preliminary bioassay results revealed that a few title compounds exhibited good insecticidal activities against lepidopteran pests, such as Plutella xylostella, Mythimna separate, Heliothis armigera, and Ostrinia nubilalis. Some title compounds also elicited broad-spectrum insecticidal activities against dipterous insects including Culex pipiens pallens after altering the amide position. Similar to pyrazole-5-carboxamide analogues, compounds 6b and 6e showed 100% insecticidal activity against P. xylostella, C. pipiens pallens, and M. separate at concentrations of 200, 2, and 200 mg/m L, respectively.This finding suggested that 5-(trifluoromethyl)-1H-pyrazole-4-carboxamide derivatives are potential alternative insecticides for management of agriculture pests.     

Design,Synthesis and Insecticidal Activities of Novel 5-Alkoxyfuran-2(5H)-one Derivatives

A series of novel 5?alkoxyfuran-2(5H)-one derivatives was synthesized, and characterized by 1H NMR, 13C NMR and HRMS. Biological activities of all the title compounds were evaluated systematically. Preliminary bioassays indicated that most of the compounds exhibited moderate insecticidal activities against Aphis craccivora and Nilaparvata lugens at 100 mg/L. Compounds 4h and 4w exhibited 100% mortality rate against Aphis craccivora at 100 mg/L, and compound 4h exhibited good mortality rate against Aphis craccivora and Nilaparvata lugens (60% and 75%, respectively) even at 4 mg/L. The results demonstrated the impact of various chemical groups on insecticidal activities and provided a potential clue for further exploring novel high-effective broad-spectrum insecticides.