A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~...A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.展开更多
The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） s...The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） species is threatening agricul- tural production all over the country as resistance to commonly used insecticides has increased. This situation highlights the need for alternative pest control measures. Cyantraniliprole, a novel anthraniiic diamide insecticide, has been widely employed to control Hemipteran pests. To monitor the levels of resistance to cyantraniliprole in B. tabaci field populations in China, bioassays were conducted for 18 field samples from nine provinces over two years. Compared with median lethal concentration （LC^0） for the MED susceptible strain, all field samples had significantly higher resistance to cyantraniliprole. Furthermore, resistance factors （RFs） increased significantly in samples from Shanxi （from 5.62 in 2015 to 25.81 in 2016）, Hunan （3.30 in 2015 to 20.97 in 2016） and Hubei （from 9.81 in 2015 to 23.91 in 2016） provinces. This study indicates a considerable decrease in the efficacy of cyantraniliprole against B. tabaci and establishes a baseline of susceptibility that could serve as a reference for future monitoring and management of B. tabaci resistance to cyantraniliprole.展开更多
Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral ant...Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral anthranilic diamides were designed by introducing the D-alanine acid and D-serine acid esters as well as trifluoroethoxyl group into the anthranilic diamide skeleton and synthesized successfully based on anthranilic diamide and FKI-1033 structures. The structures of the title compounds Ia–i and IIa–i were confirmed by melting points,~1H NMR,^（13）C NMR, elemental analysis and specific optical rotation analysis.The preliminary bioassay results indicated that most of the title compounds exhibited considerable larvicidal activities against oriental armyworm at 10 mg/L, especially Ib, Ie and IIh showed remarkable insecticidal activities at 0.5 mg/L. The larvicidal activity against diamondback moth of Ia and IId were 80%and 90% respectively at 0.0001 mg/L, which was similar to that of chlorantraniliprole. The relationship between structure and insecticidal activity was analyzed to reveal a possible co-regulated effect of the chiral amino acid ester, halogen atom or cyano group, and trifluoroethyloxyl group of the skeleton structures of the title compounds, which will provide useful information for guiding the design and discovery of new RyRs activators and insecticidal agrochemicals.展开更多
以对氟苯甲酸和取代邻氨基苯甲酸为起始原料,设计并合成11个含氟基苯并噻唑基邻甲酰氨基苯甲酰胺类化合物,其结构经1 H NMR、13C NMR、IR及元素分析确证.初步生物活性测试结果表明,在500mg/L浓度下部分化合物对烟草花叶病毒(TMV)有一定...以对氟苯甲酸和取代邻氨基苯甲酸为起始原料,设计并合成11个含氟基苯并噻唑基邻甲酰氨基苯甲酰胺类化合物,其结构经1 H NMR、13C NMR、IR及元素分析确证.初步生物活性测试结果表明,在500mg/L浓度下部分化合物对烟草花叶病毒(TMV)有一定抑制作用.采用MTT法进行化合物抑制PC3及Bcap-37癌细胞体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3和Bcap-37癌细胞活性,其中化合物4d在10μmol.L-1浓度下对PC3和及Bcap-37的抑制率分别为73.2%和68.1%.展开更多
The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rar...The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.展开更多
A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of ...A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of organic base. The obtained imidodicarbonic diamides were demonstrated by X-ray diffraction analysis.展开更多
Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diami...Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diamides are still unclear until now. In the present study, DFT-based potential energy surface scanning was used to detect the low energy conformations of chlorantraniliprole, then were used respectively in the structure alignment for a series of anthranilic diamide compounds followed by detailed CoMFA and CoMSIA analyses. Finally, the bioactive conformations of anthranilic diamide insecticides were revealed from a series of low energy conformations, which might provide some clues for future insecticide design.展开更多
To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activiti...To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activities were evaluated and the preliminary struc ture-activity relationships(SARs)were discussed.The insecticidal results showed that some of the compounds(8a-8h,8m,8n)exhibited good larvicidal activities against oriental armyworm at 2.5 mg·L^(-1),and compound 8m possessed 60%insecticidal activityat 0.5 mg·L^(-1).For diamondback moth,8m exhibited better activity than Chlorantraniliprole at a hundred fold preference.展开更多
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 N...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,-（13）C NMR,-（19）F NMR,elemental analysis,HRMS or mass spectra.Their insecticidal activities against oriental armyworm（Mythimna separata） and diamondback moth（Plutella xyiostella）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.展开更多
In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H...In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that some title compounds exhibited excellent insecticidal activities against Mythimna separata, Spodoptera exigua, and Plutella xylostella. The title compound 3-nitro-N-cyclopropyl-N＇-[2-methyl-4-（perfluoropropan-2-yl）phenyl]phthalamidte （4a） was more efficient against diamondback moths than the control （chlorantraniliprole）. The effects of some title compounds on intracellular calcium of neurons from the Spodoptera exigua proved that the title compounds were RyR activators.展开更多
Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal act...Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal activity, two series of N-pyridylpyrazole derivatives containing N-(tert-butyl)benzohydrazide substructures were designed and synthesized. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. Preliminary bioassay results revealed that some of the new compounds exhibited good insecticidal activity against the oriental armyworm and diamondback moth. The mode of action of these compounds were verified using calcium-imaging technique and the results showed that some new compounds could effectively modulate the insect cytosolic Ca^2+ level, and break the cellular calcium homeostasis, indicating some of these compounds were potent activators of the RyRs.展开更多
基金supported by National Basic Research Program of China(973 Program,No.2010CB126100)National High Technology Research and Development Program of China (863 Program,No.2011AA10A207)supported by National Key Technology R&D Program of China(No. 2011BAE06B01)
文摘A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.
基金supported by the National Natural Science Foundation of China (31601635)the Beijing Natural Science Foundation,China (6174038)the earmarked fund for Beijing Innovation Consortium of Agriculture Research System,China (BAIC07-2017)
文摘The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） species is threatening agricul- tural production all over the country as resistance to commonly used insecticides has increased. This situation highlights the need for alternative pest control measures. Cyantraniliprole, a novel anthraniiic diamide insecticide, has been widely employed to control Hemipteran pests. To monitor the levels of resistance to cyantraniliprole in B. tabaci field populations in China, bioassays were conducted for 18 field samples from nine provinces over two years. Compared with median lethal concentration （LC^0） for the MED susceptible strain, all field samples had significantly higher resistance to cyantraniliprole. Furthermore, resistance factors （RFs） increased significantly in samples from Shanxi （from 5.62 in 2015 to 25.81 in 2016）, Hunan （3.30 in 2015 to 20.97 in 2016） and Hubei （from 9.81 in 2015 to 23.91 in 2016） provinces. This study indicates a considerable decrease in the efficacy of cyantraniliprole against B. tabaci and establishes a baseline of susceptibility that could serve as a reference for future monitoring and management of B. tabaci resistance to cyantraniliprole.
基金supported by the National Natural Science Foundation of China(Nos. 21772103, 21602118)the National Key Research and Development Program of China (No. 2017YFD0200505)Tianjin Natural Science Foundation (No. 17JCYBJC19900)
文摘Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral anthranilic diamides were designed by introducing the D-alanine acid and D-serine acid esters as well as trifluoroethoxyl group into the anthranilic diamide skeleton and synthesized successfully based on anthranilic diamide and FKI-1033 structures. The structures of the title compounds Ia–i and IIa–i were confirmed by melting points,~1H NMR,^（13）C NMR, elemental analysis and specific optical rotation analysis.The preliminary bioassay results indicated that most of the title compounds exhibited considerable larvicidal activities against oriental armyworm at 10 mg/L, especially Ib, Ie and IIh showed remarkable insecticidal activities at 0.5 mg/L. The larvicidal activity against diamondback moth of Ia and IId were 80%and 90% respectively at 0.0001 mg/L, which was similar to that of chlorantraniliprole. The relationship between structure and insecticidal activity was analyzed to reveal a possible co-regulated effect of the chiral amino acid ester, halogen atom or cyano group, and trifluoroethyloxyl group of the skeleton structures of the title compounds, which will provide useful information for guiding the design and discovery of new RyRs activators and insecticidal agrochemicals.
文摘以对氟苯甲酸和取代邻氨基苯甲酸为起始原料,设计并合成11个含氟基苯并噻唑基邻甲酰氨基苯甲酰胺类化合物,其结构经1 H NMR、13C NMR、IR及元素分析确证.初步生物活性测试结果表明,在500mg/L浓度下部分化合物对烟草花叶病毒(TMV)有一定抑制作用.采用MTT法进行化合物抑制PC3及Bcap-37癌细胞体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3和Bcap-37癌细胞活性,其中化合物4d在10μmol.L-1浓度下对PC3和及Bcap-37的抑制率分别为73.2%和68.1%.
文摘The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.
基金the Natural Science Foundation of Zhejiang Province(No.LY13B020015)the Science and Technology Plan Project of Taizhou(No.131KY03)for financial support
文摘A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of organic base. The obtained imidodicarbonic diamides were demonstrated by X-ray diffraction analysis.
基金the financial support from the National Key Technology R&D Program of China (No.2011BAE06B05)
文摘Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diamides are still unclear until now. In the present study, DFT-based potential energy surface scanning was used to detect the low energy conformations of chlorantraniliprole, then were used respectively in the structure alignment for a series of anthranilic diamide compounds followed by detailed CoMFA and CoMSIA analyses. Finally, the bioactive conformations of anthranilic diamide insecticides were revealed from a series of low energy conformations, which might provide some clues for future insecticide design.
基金The project was supported by the National Key Research Program-The Innovation of Eco-Modulator of Insect Ryanodine Re-ceptor(Nos.2018YFD0200100,2017YFD0200505)the National Natural Science Foundation of China(Nos.31972287,21602118).
文摘To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activities were evaluated and the preliminary struc ture-activity relationships(SARs)were discussed.The insecticidal results showed that some of the compounds(8a-8h,8m,8n)exhibited good larvicidal activities against oriental armyworm at 2.5 mg·L^(-1),and compound 8m possessed 60%insecticidal activityat 0.5 mg·L^(-1).For diamondback moth,8m exhibited better activity than Chlorantraniliprole at a hundred fold preference.
基金financially supported by the National Natural Science Foundation of China(No.21372133)973 Program(No.2010CB126106)"111" Project of Ministry of Education of China(No.B06005)
文摘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,-（13）C NMR,-（19）F NMR,elemental analysis,HRMS or mass spectra.Their insecticidal activities against oriental armyworm（Mythimna separata） and diamondback moth（Plutella xyiostella）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.
基金Supporting information for this article is available on the WWW under http：//dx.doi.org/10.1002/cjoc.2011 00745 or from the author.Acknowledgement This work was supported by the National Natural Science Foundation of China （No. 20872069）, National Basic Research Program of China （No. 2010CB126106）, the National Key Technologies R＆D Program （No. 2011BAE06B05） and Tianjin Natural Science Foundation （No. 11JCYBJC08600）
文摘In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that some title compounds exhibited excellent insecticidal activities against Mythimna separata, Spodoptera exigua, and Plutella xylostella. The title compound 3-nitro-N-cyclopropyl-N＇-[2-methyl-4-（perfluoropropan-2-yl）phenyl]phthalamidte （4a） was more efficient against diamondback moths than the control （chlorantraniliprole）. The effects of some title compounds on intracellular calcium of neurons from the Spodoptera exigua proved that the title compounds were RyR activators.
基金the NSFC/China (No.21502229)Tianjin Natural Science Foundation (No.16JCYBJC29400).
文摘Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal activity, two series of N-pyridylpyrazole derivatives containing N-(tert-butyl)benzohydrazide substructures were designed and synthesized. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. Preliminary bioassay results revealed that some of the new compounds exhibited good insecticidal activity against the oriental armyworm and diamondback moth. The mode of action of these compounds were verified using calcium-imaging technique and the results showed that some new compounds could effectively modulate the insect cytosolic Ca^2+ level, and break the cellular calcium homeostasis, indicating some of these compounds were potent activators of the RyRs.
