Design,Synthesis and Biological Activities of Novel Anthranilic Diamides Containing Dihydroisoxazoline and Isoxazole

Anthranilic diamides are one of the most important classes of modern agrochemical insecticides. To discover new structures with higher activity, lower toxicity and lower residue, a series of novel anthranilic diamides containing dihydroisoxazoline and isoxazole was designed and synthesized. Their structures were characterized by means of melting points, proton nuclear magnetic resonance(¹H NMR), ¹³C NMR and high resolution mass spec-trometry(HRMS). According to the bioassay data, it was found that some of the title compounds exhibit moderate insecticidal activity and good antifungal activity. In particularly, compound 15b with a concentration of 50 mg/L shows a lethality rate of 60.0% against Mythimna separata Walker and a lethality rate of 50.0% against Culex pipiens pallens with a concentration of 1mg/L. Moreover, compound 15b showed good antifungal activities(58.8%, 77.1%, 70.7%, 55.3%, 60.7%, 65.4%) when against all the tested fungi(Cercospora arachidicola Hori, Physalospora piricola, Rhizoctonia cerealis, Bipolaris maydis, Watermelon anthracnose, Fusarium moniliforme). The effects of compounds 14h, 14j and 15b on the concentration of intracellular calcium ion([Ca²⁺]_i) in the central neurons of Mythimna separate Walker were well investigated via calcium imaging technique. The results demonstrate that the novel compounds can elevate the calcium concentration in the neurons, denoting that some new structures are potential modulators of the insect ryanodine receptor(RyR).     

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%.     

Design,Synthesis and Insecticidal Activity of Novel Anthranilic Diamides Containing Oxime Ester and Diacylhydrazine Moieties

Two series of novel anthranilic diamides containing oxime ester and diacylhydrazine moieties were designed and synthesized.Their structures were characterized by melting points,1H NMR,13C NMR and high resolution mass spectrometry（HRMS）.The single crystal structure of compound 7e was determined by X-ray diffraction and their evaluated insecticidal activity against oriental armyworm（Mythimna separata） indicates that some of the compounds exhibited moderate insecticidal activities.Among the 20 compounds,6a and 6b show 100％ larvicidal activity against Mythimna separate Walker at the test concentration of 100 mg/L.     

Design,Synthesis and Biological Activities of Novel Amides (Sulfonamides) Containing N-Pyridylpyrazole

In search of environmentally benign insecticides with high activity, low toxicity and low residual effects, a series of novel amides (sulfonamides) containing N‐pyridylpyrazole were designed and synthesized. Their chemical structures were characterized by ¹H NMR, MS and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activities against Mythimna separata Walker and Culex pipiens pallens.     

Synthesis and Insecticidal Activity of Novel N‐Pyridylpyrazole Carbonyl Thioureas

A series of novel N‐pyridylpyrazole carbonyl thioureas were designed and synthesized. Their structures were characterized by melting points, ¹H NMR, IR and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activity against Mythimna separata Walker and Culex pipiens pallens. Among 17 compounds, 5n and 5p showed 100% larvicidal activity against Mythimna separata Walker at the test concentration of 100 mg/L.     

Synthesis,Crystal Structure and Biological Activities of Novel Anthranilic(Isophthalic) Acid Esters

In search of environmentally benign insecticides with high activity, low toxicity and low resistance, a series of novel anthranilic(isophthalic) acid esters was designed and synthesized based on the structure of ryanodine modulating agent. All the compounds were characterized by ¹H NMR spectra, elemental analysis or high resolution mass spectrometry(HRMS). The preliminary results of biological activity assessment indicate that some of the title compounds exhibit certain but unremarkable insecticidal activity against Mythimna separata Walker at 200 mg/L and fungicidal activities against five funguses at 50 mg/L.     

Design, Syntheses and Biological Activities of Novel Anthranilic Diamide Insecticides Containing N-Pyridylpyrazole

In search of environmentally benign insecticides with high activity, low toxicity and low residue, a series of novel anthranilic diamide derivatives containing N-pyridylpyrazole was designed and synthesized. All the compounds were characterized by ¹H NMR spectroscopy and elemental analysis. The single crystal structure of compound 8j was determined by X-ray diffraction. The insecticidal activities of the new compounds were evaluated. The results show that some compounds exhibited moderate insecticidal activities against Lepidoptera pests. Among this series of compounds, compounds 8o and 8p showed 100% larvicidal activity against Mythimna separate Walker, Plutella xylostella Linnaeus and Laphygma exigua Hubner at a test concentration of 200 mg/kg, which is equal to the commercial chlorantraniliprole.     

Design,Synthesis and Insecticidal Activities of Novel Phenyl Substituted Isoxazolecarboxamides

Thirteen novel phenyl substituted isoxazolecarboxamides were synthesized, and their structures were characterized by ¹H NMR, elementary analysis and high-resolution mass spectrometry(HRMS) techniques. Their evaluated insecticidal activities against oriental armyworm(Mythimna separata) indicate that the phenyl substituted isoxazolecarboxamides exhibited moderate insecticidal activities, among which compounds 9c and 9k showed comparatively higher activities.     

Design,synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety

In order to discover new molecules with good insecticidal activities, a series of anthranilic diamides containing polyfluoroalkyl pyrazole were designed and synthesized, and their structures were characterized by ¹H NMR and HRMS. Bioassays demonstrated that some of the title compound exhibited excellent insecticidal activities. The larvicidal activities of compound 8a, 8c, 8g, 8k and 8l against Mythimna separata Walker were 100% at 0.8 mg/L. The insecticidal activities of compound 8a, 8c, 8e, 8g, 8k and 8l against Plutella xylostella Linnaeus were 100% at 0.4 mg/L. Surprisingly compounds 8a and 8c still showed 100% larvicidal activities against Plutella xylostella Linnaeus at 0.08 mg/L comparable to the commercialized Chlorantraniliprole. The LC₅₀ of compound 8a and 8c against M. separata is 0.048 and 0.043 mg/L respectively.     

Design,synthesis and insecticidal activities of novel anthranilic diamides containing fluorinated groups as potential ryanodine receptors activitors

In order to search for novel potent and environmentally benign insecticides, a series of anthranilic diamides containing various fluorinated groups were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR, ¹⁹F NMR, elemental analysis, HRMS or mass spectra. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. The preliminary structure-activity relationship (SAR) was discussed in detail. The biological assay indicated that most of the compounds exhibited moderate to excellent insecticidal activities. Especially, Ia showed high larvicidal activity against oriental armyworm. Meanwhile, Iu had better larvicidal effects against diamondback moth than commercial chlorantraniliprole.     

多卤代苯甲酰基脲类几丁质抑制剂的合成及杀虫活性多卤代苯甲酰基脲类几丁质抑制剂的合成及杀虫活性

从易得原料百菌清1出发, 经过氟交换、氨解、水解、脱羧和酰化反应, 合成得到10个新的多卤代苯甲酰基脲类几丁质抑制剂衍生物, 总收率为30%～50%. 所有化合物经¹H NMR, HREIMS, IR光谱证实. 对化合物进行了生物活性筛选, 结果表明该类化合物对粘虫和蚊幼虫均有一定的杀虫活性.     

The exploration of chiral N-cyano sulfiliminyl dicarboxamides on insecticidal activities

Due to new mechanism of action and ecofriendly characteristics,dicarboxamide insecticides have attracted more and more attentions in modern pest management.A series of 20 dual chiral N-cyano sulfilimines containing two centers(carbon and sulfur) were designed and synthesized.All title compounds were determined by ~1H NMR,high-resolution mass spectrometry(HRMS) and optical polarimeter.The preliminary results indicated that some of them exhibited favourable insecticidal activities against oriental armyworm(Pseudaletia separata Walker).These isomers exhibited different impact on activity following the sequence as(Sc,Ss) (Sc,Rs),and the rule of title compounds' activity against oriental armyworm was 3-CF_3≥2—CH_3—4—Cl2,3,4-trifluro in the anilide moiety.The results indicated that these groups such as 3-CF_3,2—CH_3—4—Cl or 2,3,4-trifluro were inefficient to replace heptafluoroisopropyl group for high larvicidal activity,which provided some guidance for the further modifications of sulfiliminyl dicarboxamides.     

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.     

Synthesis and biological activities of(E)-β-farnesene analogues containing 1,2,3-thiadiazole

In order to discover novel compounds with high-activity to control aphid,a series of novel(E)-β-farnesene analogues containing 1,2,3-thiadiazole were designed and synthesized,and their structures were confirmed by IR,~1H NMR,~(13)C NMR,and HRMS(ESI).The stability of representative compounds was studied by HPLC and ~1H NMR techniques.Repellent activity results indicated that compounds 8h and 8j displayed 60.3%and 62.0%repellent rates,respectively.The aphicidal bioassay results showed that most analogues exhibited considerable aphicidal activity against Myzus persicae.Especially,analogues 81,8s and 8t exhibited high activity with LC_(50) values of 33.4 μg/mL,50.2 μg/mL and 61.8 μg/mL,respectively,which were higher than the lead compound(E)-β-farnesene,but lower than commercial insecticide pymetrozine with a LC_(50) of 7.1 μg/mL     

含噻二唑基哒嗪酮类化合物的合成及杀虫活性

含噻二唑基哒嗪酮类化合物的合成及杀虫活性     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

O—芳基—O—烷基—O—（1—甲硫基乙叉胺基）磷酸酯的合成？…

以盐酸羟胺、乙醛、取代酚类及烷氧基磷酰二氯为原料,合成了２２个Ｏ－芳基－Ｏ－烷基－Ｏ－（１－甲硫基乙叉胺基）磷酸酯化合物,采用元素分析、红外光谱和＾１ＨＮＭＲ谱对其进行了表征。初步生物活性测定结果表明,部分化合物具有一定的杀菌、除草活性,许多化合物具有优良的杀虫活性。     

新型瑞香酮类似物的合成及杀菌活性

以瑞香狼毒中分离的天然产物(E)-1,5-二苯基-2-烯-1-戊酮(A)为先导, 引入色酮片段设计合成了15个新型的瑞香酮类似物, 其结构均经IR, ¹H NMR, ¹³C NMR及元素分析或HRMS确证. 杀菌活性测试结果表明, 在100 mg/mL浓度下, 部分化合物的杀菌活性优于先导化合物A, 其中化合物6d对水稻纹枯病菌和黄瓜灰霉病菌的抑制率分别为87%和86%, 与对照药剂苯醚甲环唑相当, 值得进一步优化研究.     

三唑酰胺1,4-戊二烯-3-酮衍生物的合成及生物活性

以丙酮和水杨醛为起始原料,设计合成了9个新型含氟1,2,4-三唑酰胺姜黄素类化合物,通过¹H NMR、¹⁹F 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。     

新型含N-吡啶基吡唑杂环的邻氨基苯甲酸酯类化合物合成，结构及生物活性研究

设计,合成了8个新的含N-吡啶基吡唑杂环的邻氨基苯甲酸酯类化合物,结构经FTIR, MS, 1H NMR 和元素分析确证,并且采用X-射线衍射分析方法确证了具有较好生物活性的化合物14d的结构。并且对这些化合物进行了杀虫活性测试,结果表明目标化合物在200 µg·mL-1对粘虫 (Mythimna separata Walker)具有一定的杀虫活性,其中14d,14f,14h在1 µg·mL-1对淡色库蚊（Culex pipiens pallens）具有很好的杀幼虫活性。