Synthesis and Insecticidal Activities of cis‐Configuration Nitenpyram Analogues with Benzoyl Hydrazines

To research on the structure–activity relationships of our designed neonicotinoid compounds, a series of novel cis‐configuration nitenpyram analogues with benzoyl hydrazines were designed and synthesized. The structures of all compounds were confirmed by IR, ¹H NMR, MS, and elemental analysis. Preliminary bioassays indicated that all the analogues exhibited good insecticidal activities against Nilaparvata legen and Aphis medicagini at 500 mg L^?1.     

Synthesis and Insecticidal Activities: cis‐Nitenpyram Analogs with 1,4‐Dihydropyridine Scaffold

By means of multicomponent reactions, via Michael addition, nucleophilic addition, using nitenpyram, substituted aromatic aldehydes, and cyanoacetate compounds or propanedinitrile, a new series of cis‐configuration nitenpyram analogs ( 1a‐1k ) were synthesized by introducing the 1,4‐dihydropyridine scaffold pharmacophore, as shown in Scheme 1. The structures of all compounds were confirmed by IR, ¹HNMR, ¹³C NMR, and elemental analysis. The preliminary bioassay showed that most of the target compounds exhibited good mortality against Aphis craccivora at 500 mg/L.     

Synthesis and Insecticidal Activity of Nitenpyram Analogs with Tetrahydropyrimidine Fixed (Z)‐Configuration

Two series of novel (Z)‐nitenpyram analogs 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , 3a , 3b , 3c , 3d were synthesized by introducing various amino acids benzyl ester or amino acids tetrahydrofurfur‐2‐yl ester into nitenpyram and forming a tetrahydropyrimidine ring to fix (Z)‐configuration. The structures of the target compounds were characterized by ¹HNMR, MS, IR, and elemental analysis. Preliminary bioassays against Nilaparvata lugens indicated that all the nitenpyram analogs exhibited good insecticidal activity at 100 mg/L, whereas the compounds 3b and 3d afforded the best in vitro inhibitory activities that had ≥ 90% mortality at 20 mg/L.     

Synthesis and Insecticidal Evaluation of Chiral Neonicotinoids Analogs: The Laurel Wilt Case

Xyleborus sp beetles are types of ambrosia beetles invasive to the United States and recently also to Mexico. The beetle can carry a fungus responsible for the Laurel Wilt, a vascular lethal disease that can host over 300 tree species, including redbay and avocado. This problem has a great economic and environmental impact. Indeed, synthetic chemists have recently attempted to develop new neonicotinoids. This is also due to severe drug resistance to “classic” insecticides. In this research, a series of neonicotinoids analogs were synthesized, characterized, and evaluated against Xyleborus sp. Most of the target compounds showed good to excellent insecticidal activity. Generally, the cyclic compounds also showed better activity in comparison with open-chain compounds. Compounds R-13, 23, S-29, and 43 showed a mortality percent of up to 73% after 12 h of exposure. These results highlight the enantioenriched compounds with absolute R configuration. The docking results correlated with experimental data which showed both cation-π interactions in relation to the aromatic ring and hydrogen bonds between the search cavity 3C79 and the novel molecules. The results suggest that these sorts of interactions are responsible for high insecticidal activity.     

cis‐Nitenpyram Analogues Containing 1,4‐Dihydropyridine: Synthesis,Insecticidal Activities,and Molecular Docking Studies

A novel series of cis‐nitenpyram analogues ( 2a – 2p ) were designed and prepared by introducing the 1,4‐dihydropyridine, with their cis‐configuration confirmed by X‐ray diffraction. Preliminary bioassays showed that most compounds exhibited good insecticidal activities at 20 mg/L against Aphis medicagini, and analogues 2a and 2d afforded the best activity, and both of them had 100% mortality at 4 mg/L. In addition, molecular docking studies were also performed to model the ligand‐receptor complexes, and the results explained the structure‐activity relationships observed in vitro, which may provide some useful information for future design of new insecticides.     

Synthesis,Insecticidal Assay and Molecular Docking Study of Novel Neonicotinoids N‐Oxide Analogues

Eight novel neonicotinoids N‐oxide analogues were designed and synthesized. All the compounds have been identified by ¹H NMR and HRMS. The N‐oxide analogues exhibit high insecticidal activity against cowpea aphids (Aphis craccivora) at 250 mg·L^?1. The influence of N‐oxide formation on the biological activity was elucidated by computational chemical study, and it indicated that the water bridge hydrogen bonding network was broken due to the influence of the O atom connected with the pyridine ring.     

新型茼蒿素类似物的合成和抗虫构效关系研究

Twenty-one tonghaosu analogs were synthesized via hydroamination or selective reduction of the endocyclic double bond of the corresponding dienol spiroketals. Structures of all the new compounds were confirmed by ^1H NMR, IR, MS, HREIMS or elemental analysis. Their antifeedant activity against large white butterfly （Pieris brassicae L） and larvicidal activity toward mosquito （Culex quinquefasciatus Say） were examined. Some of them exhibited antifeeding activities comparable to or stronger than tonghaosu Z-1. Based on the activity data, the preliminary structure-activity relationship was also discussed, which might be instructive for finding out lead compounds with better bioactivities in the future.     

含4-噻唑啉酮环的新烟碱类化合物的合成及生物活性

根据生物等排原理和新烟碱类化合物与乙酰胆碱酯酶的作用机理, 以4-噻唑啉酮(4)为中间体设计合成了2-取代-3-(2-氯-5-吡啶亚甲基)-4-氰基亚胺基-1,3-噻唑烷(8a~8c)和5-芳基次甲基-2-芳基-3-(2-氯-5-吡啶亚甲基)-4-噻唑啉酮(5a~5e)两类化合物. 中间体(4)由醛、胺和巯基乙酸缩合得到. 所有化合物的结构均经元素分析和1H NMR确证. 初步生物活性试验结果表明, 部分化合物具有一定的杀菌活性和促进黄瓜子叶生根活性, 化合物8b显示出很好的抗HIV-1蛋白酶活性.     

伞型酮类似物的合成及抗菌作用

2-甲基间二酚或5-甲基间二酚分别与dl-苹果酸或乙酰乙酸乙酯, 在浓硫酸催化下, 经Peachmann缩合反应得到伞型酮(7-羟基香豆素)类似物5～7. 5～7经甲基化得新化合物5a, 6a和7a; 经Williamson反应, TBAB(四正丁基溴化铵)相转移催化合成了14个新的香豆素类化合物5b～5e, 6b～6f, 7b～7f. 经IR, MS, ¹H NMR及元素分析对所有化合物的结构进行了表征. 初步生物活性实验结果表明, 在50 μg/mL浓度下, 化合物6对辣椒疫霉病菌(Phytophythora capsici)抑制率达58.5%, 化合物7c对番茄灰霉病菌(Botrytis cinerea)抑制率为54.0%, 化合物6c对水稻纹枯病菌(Rhizoctonia solani)的抑制率达83.7%.     

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.     

Synthesis and Insecticidal Activities of 1,5‐Disubstituted‐1,3,5‐hexahydrotriazine‐2‐N‐nitroimines

By extracting active moieties from typical insecticides and recombining to a same molecule, a series of novel title compounds were designed and synthesized as shown in Scheme 1. The structures of all compounds were confirmed by IR, ¹H NMR, MS, and elemental analysis. The preliminary bioassay showed that the partial target compounds gave 90% mortality against Tetranychus cinnabarnus at 500 mg/L.     

Synthesis and Insecticidal Activities of 1,3,5‐Trisubstituted‐1,3,5‐hexahydrotriazine‐2‐N‐nitroimines

A new series of 1,3,5‐trisubstituted‐1,3,5‐hexahydrotriazine‐2‐N‐nitroimines ( 3a – 3j ) were designed and synthesized as novel neonicotinoid analogues, and their structures were characterized by ¹H NMR, IR, elemental analysis and MS. The preliminary bioassay tests showed that most of the target compounds had good insecticidal activities against Nilaparvata lugens as well as Aphis medicaginis at 500 mg/L, while compound 3i had 100% mortality against Nilaparvata lugens at 20 mg/L.     

双酰基脲新化合物的合成与杀虫活性

报道了含双酰基脲新化合物的合成，经元素分析、IR、^1HNMR确定了新化合物的结构，部分化合物具有良好杀虫活性。     

Efficient Synthesis and Antitumor Activities of Indioside E Analogs

An efficient synthesis of seven analogs of a naturally occurring saponin, indioside E, is described. The synthesis used a 3,4,6-O-protected D-galactopyranosyl thioglycoside as the key intermediate to enable regioselective glycosylation and one-pot multistep reactions. Antitumor activities of the synthetic saponins against a human hepatocellular carcinoma cell line BEL-7402 and a human breast adenocarcinoma cell line MCF-7 were evaluated by means of the CCK-8 assay. Analogs carrying trisaccharides with the D-xylopyranose in indioside E substituted with a D-ribopyranose and an L-arabinopyranose or with its diosgenin aglycon replaced with tigogenin exhibited similar antitumor activities as indioside E, but not other analogs.     

1,5-二取代六氢三嗪-2-N-硝基亚胺的合成和杀虫活性的测定

以S-甲基-N-硝基异硫脲、取代苄胺为原料,依次经过亲核取代反应,Mannich反应合成了12个未见文献报道的1,5-二取代六氢三嗪-2-N-硝基亚胺(2a～21),结构经1H NMR,IR和元素分析确证.初步的杀虫活性测试表明,该类化合物在500mg/L时对稻飞虱具有较好的杀虫活性.     

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.     

Synthesis and optical properties of cis‐dibenzothiazolyldibenzo‐24‐crown‐8

New crown ether carrying two fluorionophores of cis‐dibenzothiazolyldibenzo‐24‐crown‐8 was synthesized from cis‐diformyldibenzo‐24‐crown‐8 and 2‐aminobenzenethiol. The binding behavior and the optical properties of the crown ether were examined through UV‐visible spectroscopy and fluorescence spectroscopy. When complexed with Na⁺, K⁺, Rb⁺, and Cs⁺ ions, it led to intramolecular charge transfer and caused the changes of the fluorescence spectra. The protonation of the crown ether was also studied. With protonation using CF₃COOH, the absorption bands and the fluorescence spectroscopy changed, the maximal fluorescence wavelengths red shifted and the fluorescence intensity with the maximum at 433 nm enhanced strongly. J. Heterocyclic Chem., (2011).     

Synthesis and Insecticidal Activities of Novel Phthalic Acid Diamides

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]phthalamide ( 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.