Synthesis and insecticidal activity of benzoheterocyclic analogues of N'-benzoyl-N-(tert-butyl)benzohydrazide: Part 3. Modification of N-tert-butylhydrazine moiety

Nineteen analogues were synthesized by modifying the tert-butylhydrazine moieties of N'-tert-butyl-N'-(3,5-dimethylbenzoyl)-5-methyl-2,3-dihydro-1,4-benzodioxine-6-carbohydrazide and N'-tert-butyl-N'-(3,5-dimethylbenzoyl)-5-methylchromane-6-carbohydrazide (chromafenozide), and the synthesized analogues were evaluated for their insecticidal activity against Spodoptera litura F. While all of the synthesized analogues had insecticidal activity inferior to those of the lead compounds, several of the analogues nonetheless showed high insecticidal activity. Chromafenozide has shown very high selectivity toward lepidopteran species.     

Synthesis and insecticidal activity of benzoheterocyclic analogues of N'-benzoyl-N-(tert-butyl)benzohydrazide: Part 2. Introduction of substituents on the benzene rings of the benzoheterocycle moiety

A series of N'-benzoheterocyclecarbonyl-N-tert-butyl-3,5-dimethylbenzohydrazide analogues possessing a variety of substituents on the benzene rings of the benzoheterocyle moieties were synthesized and tested for their insecticidal activity. The introduction of a methyl group at the R1 position of the benzoheterocycle moiety strongly increased the insecticidal activity. Among the analogues synthesized, N'-tert-butyl-N'-(3,5-dimethylbenzoyl)-5-methyl-6-chromanecarbohydrazide showed the highest insecticidal activity (LC50 = 0.89 mg litre(-1)).     

Synthesis and insecticidal properties of derivatives of propane-1, 3-dithiol (analogues of the insecticidal derivatives of dithiolane and trithiane from the alga Chara globularis Thuillier)

Functional derivatives of 2-(methylthio)propane-1, 3-dithiol (open chain analogues of the insecticidal 4-methyithio-1, 2-dithiolane and 5-methylthio-1, 2, 3-trithiane from the alga Chara globularis) possess insecticidal properties similar to those of the structurally related nereistoxin. Some derivatives of propane-1, 3-dithiol, bearing 2-substituents different from the methylthio group, have also been shown to have insecticidal pioperties.     

辣椒碱类似物的合成及杀虫活性

基于辣椒碱结构,以取代苄胺为原料,经N-酰化反应合成了6个系列204个辣椒碱类似物,其中8个为新化合物。通过核磁共振氢谱 (1H NMR) 对化合物的结构进行了确证。采用叶碟法测定了目标化合物的杀虫活性。结果表明:大部分化合物在10 μg/ 片下对供试的3龄东方黏虫Mythimna separata有较强的毒杀活性,其中化合物 A30 、 D20 、 D30 、 D35 、 E30 和 F30 48 h的致死率达100%,化合物 D19 、 D21 、 D22 、 D23 、 D31 和 E31 48 h的致死率在90%以上。初步构效关系表明,苄胺苯环上氟原子单取代衍生物的杀虫活性优于氟原子双取代衍生物,其中以2-氟苄胺衍生物 ( D 系列) 杀虫活性较好;此外,酰基为2-噻吩甲酰时的杀虫活性明显优于其他取代基,表明酰基对该类化合物的杀虫活性也有显著影响。     

Synthesis and insecticidal activity of lipophilic amides. Part 6: 6-(disubstituted-phenyl)hexa-2,4-dienamides

By using a phosphonate containing an N-(2,2-dimethylpropyl) instead of an N-(2-methylpropyl) group, rearrangement during the Wadsworth-Emmons condensation step was restricted to an acceptable level even with products from disubstituted phenylacetaldehydes. Previous results had shown that this change in N-group did not alter insecticidal activity drastically, so structure-activity relationship conclusions could be drawn from both series in combination. The presence of methyl groups on the phenyl lowered activity, confirming results in the mono-substituted series, so attention was directed primarily to the numerous possible di-halo combinations. Many were active, especialty those with 3,4 or 3,5 substitution patterns, but beyond this no simple correlations could be detected relating position or nature of substituents to activity. Varying both the phenyl substituents and amine group gave results approximately in agreement with additivity principles.     

Lead optimization and insecticidal activity of analogues of daphneolone isolated from Stellera chamaejasme L

Starting from the chemical structure of the botanical aphicides 1,5-diphenyl-1-pentanone and 1,5-diphenyl-2-penten-1-one, extracted from Stellera chamaejasme L., the authors designed and synthesized a series of novel compounds following the concept of bioisosterism. Their structures were established on the basis of (1)H NMR and GC-MS spectra, and the insecticidal activities of the compounds were evaluated against Aphis gossypii Glover. The results demonstrated that the substitution of a heterocycle for the phenyl ring was favourable. Thus, further modification of compound 2n, containing a furan ring, which showed excellent activity (LC(50) = 0.85 g L(-1)), is of some promise.     

Insecticidal properties of benzofuran-2-carboxylic acid derivatives

A series of amides and esters of substituted benzo[b]furan-2-carboxylic acids have been synthesised, and their activity against adult sweet potato weevils, Cylas formicarius elegantulus (Summer) studied. The topical insecticidal potency of these compounds was compared in acetone solution and in a mixture of piperonyl butoxide (PB) and acetone (0·05+99·95 by volume). The compounds were much more active when administered in the acetone/PB mixture, and exhibited 48-h LD₅₀ values ranging from 1·7 to 26·6 μg per insect. The most active compound, 2-(3,5-dimethylpyrazol-1-ylcarbonyl)-6-methoxy-3-methylbenzofuran, was equiactive with technical grade dimethoate (in acetone/PB) on a weight basis. © 1998 SCI     

新型氯虫苯甲酰胺衍生物的合成及其杀虫活性

以氯虫苯甲酰胺为先导,设计并合成了一系列结构新颖的邻氨基苯甲酰胺类衍生物,其结构均经核磁共振氢谱和质谱确证。初步杀虫活性测试结果表明,在质量浓度为1μg/mL时,部分化合物对小菜蛾Plutella xylostella的致死率均超过90%,高于先导化合物氯虫苯甲酰胺。     

Interaction of dinotefuran and its analogues with nicotinic acetylcholine receptors of cockroach nerve cords

To investigate the action of dinotefuran (MTI-446, 1-methyl-2-nitro-3-(tetrahydro-3-furylmethyl)guanidine), a recently developed insecticide, on insect nicotinic acetylcholine receptors (nAChRs), we determined the potencies of the compound and 15 analogues in inhibiting the specific binding of [3H]epibatidine (EPI), a nAChR agonist, and [3H]alpha-bungarotoxin (alpha-BGT), a competitive nAChR antagonist, to the nerve cord membranes of American cockroaches (Periplaneta americana). Racemic dinotefuran inhibited [3H]EPI binding with an IC50 of 890 nM and [3H]alpha-BGT binding with an IC50 of 36.1 microM. Scatchard analysis indicated that the dinotefuran inhibition of [3H]EPI binding was a competitive one. Slight structural modification caused a drastic reduction in potency; only four analogues were found to be equipotent to or more potent than dinotefuran. Chloropyridinyl and chlorothiazolyl neonicotinoid insecticides displayed two or three orders of magnitude higher potency than dinotefuran. There was a good correlation between the IC50 values of tested compounds obtained with [3H]EPI and those obtained with [3H]alpha-BGT. A better correlation was observed between 3-h knockdown activities (KD50) against German cockroaches (Blattella germanica) and IC50 values obtained from [3H]EPI assays than between 24-h lethal activities (LD50) and IC50 values. While the results indicate that dinotefuran and its analogues interact with the ACh-binding site in cockroach nAChRs, it remains to be elucidated why they displayed lower potencies than those expected based on their insecticidal activities.     

氟吡呋喃酮及其类似物研究进展

氟吡呋喃酮 (flupyradifurone) 是拜耳公司开发的新型丁烯内酯类杀虫剂,对刺吸式口器害虫具有优异的杀虫活性,与现有商品化新烟碱类杀虫剂相比,其作用机制独特,对蜜蜂低毒,自2014年上市以来就成为了农药学研究领域的热点。本文从氟吡呋喃酮的创制过程、生物活性及抗性、作用机制、代谢残留、对蜜蜂等非靶标生物的影响以及结构修饰等方面对该产品进行了综述。     

O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate,a new experimental insecticide and acaricide

The insecticidal and acaricidal action, anti-cholinesterase activity and toxicity to rats of a new experimental pesticide, O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate ( I ), and those of some by-products found in the technical material, are described. High insecticidal and acaricidal effectiveness of I was found in laboratory and field trials. The activity as a soil insecticide in field trials was equal to, or greater than, that of other chemicals used at present.     

Synthesis and insecticidal activity of novel 1,3,4-oxadiazolin-5-one and pyrazolin-5-one derivatives

A series of novel 2-(2,4,6-trisubstituted phenyl)-1,3,4-oxadiazolin-5-one derivatives and 3-(2,4,6-trichlorophenyl)pyrazolin-5-one derivatives were synthesized and evaluated for insecticidal activity. It was found that a moderately bulky alkyl group, such as a tert-butyl group, on the heterocyclic ring, and a trifluoromethyl group on the benzene ring were optimal substituents on the molecule. The oxygen atom in the oxadiazoline ring was essential for insecticidal activity. Of the compounds assayed, 4-tert-butyl-2-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-5-one gave the highest activity against Nephtotettix cincticeps, with an LC₅₀ value of 0.51 mg litre⁻¹. © 1999 Society of Chemical Industry     

2-溴代呋喃基或噻吩基-1,3-二噻烷衍生物的合成及杀虫活性

为寻找新的环境友好型杀虫剂,用溴代呋喃甲醛和溴代噻吩甲醛分别与2-取代1,3-丙二硫醇缩合,合成了16个未见文献报道的2-溴代呋喃基或噻吩基-1,3-二噻烷衍生物。其化学结构均通过1H NMR和元素分析或质谱的确认。初步的生物活性测试结果表明,该类化合物对桃蚜Myzus persicae表现出一定的杀虫活性,其中化合物 M11 在600 μg/mL下对桃蚜的校正死亡率为90％。     

Biological characterization of sulfoxaflor, a novel insecticide

BACKGROUND: The commercialization of new insecticides is important for ensuring that multiple effective product choices are available. In particular, new insecticides that exhibit high potency and lack insecticidal cross‐resistance are particularly useful in insecticide resistance management (IRM) programs. Sulfoxaflor possesses these characteristics and is the first compound under development from the novel sulfoxamine class of insecticides. RESULTS: In the laboratory, sulfoxaflor demonstrated high levels of insecticidal potency against a broad range of sap‐feeding insect species. The potency of sulfoxaflor was comparable with that of commercial products, including neonicotinoids, for the control of a wide range of aphids, whiteflies (Homoptera) and true bugs (Heteroptera). Sulfoxaflor performed equally well in the laboratory against both insecticide‐susceptible and insecticide‐resistant populations of sweetpotato whitefly, Bemisia tabaci Gennadius, and brown planthopper, Nilaparvata lugens (Stål), including populations resistant to the neonicotinoid insecticide imidacloprid. These laboratory efficacy trends were confirmed in field trials from multiple geographies and crops, and in populations of insects with histories of repeated exposure to insecticides. In particular, a sulfoxaflor use rate of 25 g ha^?1 against cotton aphid (Aphis gossypii Glover) outperformed acetamiprid (25 g ha^?1) and dicrotophos (560 g ha^?1). Sulfoxaflor (50 g ha^?1) provided a control of sweetpotato whitefly equivalent to that of acetamiprid (75 g ha^?1) and imidacloprid (50 g ha^?1) and better than that of thiamethoxam (50 g ha^?1). CONCLUSION: The novel chemistry of sulfoxaflor, its unique biological spectrum of activity and its lack of cross‐resistance highlight the potential of sulfoxaflor as an important new tool for the control of sap‐feeding insect pests. Copyright © 2010 Society of Chemical Industry     

Design, synthesis and insecticidal activities of novel pyrazole amides containing hydrazone substructures

BACKGROUND: Pyrazole and hydrazone derivatives possess good insecticidal activities; their substructural units are widely used in pesticide design. In an effort to discover new molecules with good insecticidal activities, a series of pyrazole amide derivatives containing hydrazone substructures were synthesised and bioassayed. RESULTS: Bioassays demonstrated that some of the title compounds exhibited notable control of Plutella xylostella (Linnaeus), Helicoverpa armigera (Hübner), Culex pipiens pallens, Laphygma exigua (Hübner), Spodoptera litura (Fabricius), Nilaparvata lugens (Stål) and Rhopalosiphum maidis (Fitch) at 5, 10, 0.25, 200, 20, 100 and 500 mg L^?1 respectively. Comparative molecular field analysis (CoMFA) based on the bioactivities for P. xylostella was studied; the values of q² and r² for the CoMFA model were 0.701 and 0.964 respectively. CONCLUSION: Some of the title compounds displayed good and broad‐spectrum insecticidal activities against different insect species; the CoMFA model revealed that a bulky and negatively charged group at the 4‐position of benzene could enhance insecticidal activity. These results could provide useful information for the design of novel insecticide containing substructural units of pyrazole amide and hydrazone. Copyright © 2011 Society of Chemical Industry     

0.05%氟虫腈杀蚁饵剂对红火蚁的传毒活性测定

应用联杯法等室内测定了0.05%氟虫腈杀蚁饵剂对红火蚁的引诱力、毒杀速度及其传导毒杀活性.结果表明,供试饵剂对红火蚁的引诱性、毒杀速度显著优于正舒(对照药剂).红火蚁觅食到供试饵剂的初始时间为2.00 min,与正舒的2.33 min达显著差异;供试饵剂处理后24 h的工蚁死亡率为80.65%,显著高于对照饵剂的50.15%;72 h的工蚁死亡率即达到100%.联杯法测定结果表明,0.05%氟虫腈杀蚁饵剂能通过工蚁的取食和交哺行为进行传导.供试饵剂受药杯中工蚁、幼蚁和蚁后3 d后死亡率均达到100%,显著高于对照饵剂.0.05%氟虫腈杀蚁饵剂引诱性强、对红火蚁具有高胃毒、高传导毒杀活性,可适用于防控入侵红火蚁.     

嘧啶酮类衍生物的合成及杀虫活性

为了创制高效广谱的绿色杀虫剂,以(E)-4,5-二氢-6-甲基-4-(3-吡啶亚甲基氨基)-1,2,4-三嗪-3(2H)-酮(吡蚜酮)为先导,用带有不同电荷密度的五元、六元取代苯环或杂环取代其结构中的吡啶环部分,合成了10个全新的嘧啶酮类衍生物,特别对其中所包含的三嗪环和二氢喹唑啉酮合成部分进行了重点研究。所有目标化合物的结构均经过核磁共振氢谱、高分辨质谱及红外光谱的确认。初步杀虫活性测试结果表明,目标化合物对蚜虫Aphis craccivora未表现出明显的杀虫活性,初步暗示了先导化合物吡蚜酮结构中所含的吡啶环部分可能对其杀虫活性起了重要作用。     

Synthesis and insecticidal activity of nitroguanidine derivatives

Nitroguanidine derivatives with thiazol-5-ylmethyl moieties were prepared and their insecticidal activities against homopterous pests were tested. New synthetic routes for 2-chloro-5-chloromethylthiazole from 2,3-dichloro-1-propene and for substituted nitroguanidines from S-methyl-N-nitroisothiourea were established. Biological evaluation led to a novel insecticide (E)-1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguani dine (TI-435) which has a broad activity spectrum and is under development. ©1999 Society of Chemical Industry     

The optical isomers of α-cyano-3-phenoxybenzyl 3-(1,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclo-propanecarboxylate and their insecticidal activities

Bromination of the dichlorovinyl group of cypermethrin yielded a new compound which is a highly potent insecticide. This dibromo adduct has four asymmetric centres and therefore can exist as a mixture of 16 stereoisomers. To establish the influence of the absolute configuration at the chiral centres on the biological activities of these isomers, each of the isomers was isolated; their insecticidal activities against larvae of Heliothis virescens, and adult Calliphora erythrocephala and Blattella germanica were then determined and compared with those of (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin NRDC 161), of fenvalerate, and of the eight stereoisomers of cyper methrin.     

Effects of a Chenopodium-based botanical insecticide/acaricide on Orius insidiosus (Hemiptera: Anthocoridae) and Aphidius colemani (Hymenoptera: Braconidae)

UDA-245 is a Chenopodium-based natural insecticide. Forty-eight hours after treatment with this compound, Orius insidiosus (Say) and Aphidius colemani Viereck showed slight contact toxicity at 5 g AI liter(-1). There was no residual toxicity to A colemani. These two beneficials are currently used in commercial flower and vegetable greenhouses for the management of thrips, spider mites, aphids and small caterpillars. In contrast, abamectin and insecticidal soap were toxic by contact to both species. UDA-245 did not reduce the number of eggs laid by treated O insidiosus. The eclosion of these eggs was also not adversely affected by UDA-245. The other two insecticides, abamectin and insecticidal soap had no effect on the emergence of A colemani from treated aphid mummies. However, abamectin decreased the percentage of aphid parasitism by A colemani following a residual treatment. The LC50 for UDA-245 for the two beneficials is slightly over twice the recommended field dose.