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。     

含香豆素基团的二氯丙烯类衍生物的合成及杀虫活性

以丙二酸二乙酯、间苯二酚和1,1,3-三氯丙烯等为原料,经取代、环合、缩合等反应合成了9个含有香豆素基团的二氯丙烯类衍生物,化合物结构经IR、 1H NMR、 MS及元素分析确证。初步的生物活性测定结果表明,该类化合物在400 mg/L质量浓度下对小菜蛾Plutella xylostella有较好的杀虫活性,其中化合物 5e 对小菜蛾的致死率达到93%。     

新一代烟碱类杀虫剂呋虫胺及中间体合成新工艺的研究

本文以丙二酸二乙酯为原料,在乙醇钠条件下与氯乙酸乙酯反应生成乙烷-1,2,2-三羧酸乙酯,再用硼氢化钠还原得2-羟基-1,4-丁二醇,在对甲苯磺酸的催化下脱水环合成3-羟甲基四氢呋喃,再与对甲苯磺酰氯、三乙胺反应生成3-四氢呋喃甲基对甲苯磺酸酯;甲醛水溶液、甲基硝基胍、甲胺水溶液在乙醇中反应生成1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪;3-四氢呋喃甲基对甲苯磺酸酯与1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪反应生成呋虫胺。     

呋虫胺4%展膜油剂的配制及田间防效研究

本研究以呋虫胺为有效成分,通过对溶剂和表面活性剂的筛选和配伍,确定呋虫胺4%展膜油剂最优配方(各组分的量用质量分数表示)为:呋虫胺4%;溶剂油Green BR25%;OP-10、2201和十二碳醇酯以质量比为3:1:5复配,总质量分数为9%;油酸甲酯油62%;所配制的4%呋虫胺展膜油剂各项质量控制技术指标均合格。田间药效试验结果表明:采用呋虫胺4%展膜油剂滴施防治稻飞虱,用药量为6、8、10g(a.i.)/667m~2时,药后30d校正防效分别为85.3%,90.1%,95.7%;药后50d校正防效分别为56.2%,74.5%,83.3%。表明这种滴施省力化施药技术对稻飞虱有较好的防治效果。     

取代双吡唑类化合物的合成及杀虫活性

以3-氯苯肼盐酸盐( 1 )和1,1,3,3-四甲氧基丙烷( 2 )为起始原料,经环化、Vilsmeier反应得1-(3-氯苯基)-1H-吡唑-4-甲醛( 4);(4 )与3-三氟甲基苯乙酮( 5 )经Claisen-Schmidt缩合反应得取代芳基烯酮类化合物( 6 ),再与水合肼发生环化反应得3-(3-三氟甲基苯基)-5-(3-氯苯基-1H-吡唑)-4,5-二氢吡唑( 7),其与取代异氰酸酯 作用,制得15个未见文献报道的结构新颖的取代双吡唑类化合物。利用核磁共振氢谱(1H NMR)和质谱(MS)对其结构进行了表征。初步生物活性测定结果表明,在 500 mg/L 质量浓度下,部分化合物对小菜蛾Plutella xylostella的致死率达100%,而对苜蓿蚜Aphis medicaginis、稻褐飞虱Nilaparvata lugens、朱砂叶螨Tetranychus cinnabarinus均无杀虫活性。     

S-茚虫威的晶型研究及杀虫活性比较

为了研究S-茚虫威的多晶型现象,寻找对杀虫有效的优势晶型,采用溶剂结晶法 (异丙醇、乙醇) 制备得到S-茚虫威的一种新晶型A,并首次获得了其单晶结构;采用熔融法制备得到其无定型形式,通过X射线粉末衍射 (PXRD)、差示扫描量热分析 (DSC)、热重分析 (TGA) 及傅里叶变换红外光谱分析 (FTIR) 等技术对不同晶型结构进行了表征。进一步制备了S-茚虫威不同晶型的15%悬浮剂,并对其杀虫活性进行了对比研究。结果表明:S-茚虫威存在两种不同的晶型状态——晶型A和无定型形式,其15%无定型悬浮剂对二化螟Chilo suppressalis (Walker) 和小菜蛾Plutella xyllostella (L.) 杀虫活性显著高于其15%晶型A悬浮剂。本研究证实了S-茚虫威存在多晶型状态,且无定型形式为其活性优势晶型。     

50%呋虫胺对入侵害虫扶桑绵粉蚧的室内毒力及田间药效

【目的】为评估50%呋虫胺水分散粒剂对扶桑绵粉蚧的防治效果。【方法】采用喷雾法进行50%呋虫胺水分散粒剂的室内生物测定和田间药效试验。【结果】3龄幼虫、成虫的致死中浓度LC₅₀值分别为25.829 7 mg/L、49.589 8 mg/L,显示了对扶桑绵粉蚧有较强的毒力。田间药效试验显示,相同的处理时间,呋虫胺对扶桑绵粉蚧的防效与浓度呈正相关;C1(0.125 g/L)、C2(0.167 g/L)处理在药后7 d达到最高防效,14 d后防效下降;C3(0.2 g/L)、C4(0.25 g/L)和C5(0.5 g/L)防效与药剂浓度和处理时间呈正相关,C5的防治效果最好,药后3 d、7 d的校正防效显著高于其他浓度的同期效果,药后14 d的防效为92.08%,显著高于C1、C2和C3,与C4差异不显著。【结论】研究表明,50%呋虫胺水分散粒剂可有效防治扶桑绵粉蚧。在进行防治时,综合考虑防治效果、防治成本及生态环境保护等因素,建议使用C4进行防治,当绵粉蚧虫口基数较大时,可在药后10～14 d进行2次用药。     

含苯丙氨酸和1H-茚-1-酮类氯虫苯甲酰胺类似物的合成及杀虫活性

为了开发新的杀虫化合物,以氯虫苯甲酰胺为先导,2-甲基-3-氨基苯甲酸为起始原料,经过卤化生成5-氯-3-甲基-2-氨基苯甲酸;再与3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-甲酸进行缩合反应,生成6-氯-2-(3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-基)-8-甲基-4H-3,1-苯并噁嗪-4-酮;最后引入苯丙氨酸片段并经环化反应,分别合成了两个系列共计23 个新化合物( 4 和 5 ),其中化合物 4 为含苯丙氨酸的氯虫苯甲酰胺类似物,化合物 5 为由化合物4环化生成的含1H-茚-1-酮片段的氯虫苯甲酰胺类似物,所有化合物的结构均通过核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱(HRMS)的表征及确证。初步室内杀虫活性测试结果表明,多数目标化合物对黏虫Mythinma separata具有较高的杀虫活性,其中14个化合物在100 mg/L下对黏虫Mythinma separata的致死率为100%,化合物 5k ( 1H-茚-1-酮片段中取代基为羟基 ) 在4和0.8 mg/L下的致死率分别为90%和70%,其LC₅₀值为0.55 mg/L。分子对接结果表明,化合物 5k 与氯虫苯甲酰胺一样,也是作用于鱼尼汀受体(RyR),但与靶标结合的氨基酸残基不同,这种差异可能对黏虫的抗药性治理研究有益。     

新烟碱类杀虫剂呋虫胺对褐飞虱的防效及安全性评价

为了明确新烟碱类杀虫剂呋虫胺对水稻褐飞虱的防治效果及其对水稻及其天敌拟水狼蛛的安全性。本研究通过室内作物安全性试验,测定了呋虫胺对水稻的安全性;采用浸渍法,测定了呋虫胺对褐飞虱和拟水狼蛛的毒力,并进行了田间药效试验。室内毒力测定表明,呋虫胺对水稻褐飞虱的LC50和LC帅分别为0.761 0和4.305 5mg/L,对天敌拟水狼蛛表现一定低风险,安全系数为5.443 3;安全性评估试验表明,20%呋虫胺悬浮剂喷施后水稻未出现药害,对水稻生长没有抑制作用;大田防效的试验表明,20%呋虫胺悬浮剂推荐剂量的防效高于350g/L吡虫啉悬浮剂推荐剂量的防效,施药后1d防效达到80%以上,施药后7d防效达到90%以上。综上所述,呋虫胺对水稻褐飞虱的防治效果好,对作物安全,对天敌拟水狼蛛低风险。     

苯并吡唑类衍生物的设计、合成、杀虫活性及结合模式研究

基于新报道的高活性介离子类nAChR调节剂结构,通过骨架跃迁策略设计、合成了30个未见文献报道的苯并吡唑类化合物,所有化合物的结构均通过核磁共振氢谱(¹H NMR)、碳谱(¹³C NMR)及高分辨质谱(HRMS)确证。杀虫活性测试结果表明,目标化合物 A1 、 A7 、 A16 和 A22 在500 mg/L下对苜蓿蚜的致死率约为40%,活性弱于先导结构化合物 1 。初步分析,介离子结构与非介离子结构结合模式相近,其理化性质以及静电势表面的差异可能是导致目标化合物活性比化合物 1 低的主要原因。     

Structural effects of dinotefuran and analogues in insecticidal and neural activities

The insecticidal potencies of dinotefuran and analogues against the adult male American cockroach, Periplaneta americana (L) were measured by injection with or without metabolic inhibitors. The potency of dinotefuran was close to those of clothianidin and imidacloprid under the conditions used. The nerve-excitatory and nerve-blocking activities were measured with central nerve cords of P americana. The nerve-excitatory activity of dinotefuran was lower than that of imidacloprid, but was comparable with that of clothianidin. The nerve-blocking activity of dinotefuran was comparable with that of imidacloprid and slightly higher than that of clothianidin. Quantitative analyses showed that variations in the insecticidal activity were better correlated with variations in the nerve-blocking activity than with those in the nerve-excitatory activity when the contribution of the hydrophobic factor was allowed for.     

新型芳氧吡啶肟醚类化合物的设计、合成和杀虫活性

以芳氧吡啶乙酮分子插件为基础,设计合成了一系列芳氧吡啶乙酮肟醚类化合物,其结构经核磁共振氢谱、碳谱及高分辨质谱等确证.初步杀虫活性测定结果表明,该系列化合物对棉蚜Aphis gossypii(Glover)具有较好的杀虫活性,其中化合物5a和6i在50 μg/mL下对棉蚜的致死率分别为76.8％和70.1％,具有作为先...     

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     

Design, synthesis and structure-activity relationship of novel coumarin derivatives

BACKGROUND: The lead coumarin derivative (E)‐methyl 3‐methoxy‐2‐[2‐(4‐methylcoumarin‐7‐yloxymethyl)phenyl]acrylate was discovered by using an intermediate derivatisation method. To discover new coumarin derivatives with improved activity, a series of substituted coumarins were synthesised and bioassayed. RESULTS: The compounds were identified by ¹H NMR, IR, MS and elemental analysis. Bioassays demonstrated that some of the title compounds exhibited excellent fungicidal activity against cucumber downy mildew at 25 mg L^?1. The relationship between structure and fungicidal activity is reported. CONCLUSION: The present work demonstrates that coumarin derivatives containing methoxyacrylate moieties can be used as possible lead compounds for developing novel fungicides. Copyright © 2011 Society of Chemical Industry     

Design, synthesis and antifungal/insecticidal evaluation of novel nicotinamide derivatives

A series of nicotinamide derivatives based on Boscalid were prepared and tested for their activities against seven plant pathogenic fungi and two insects. The preliminary bioassays indicated that almost all of the synthesized target compounds displayed the antifungal activities and some of them also had certain insecticidal activities. And, compound 12 showed the strongest activity of all against Rhizoctonia solani (EC₅₀ = 0.010 mg L⁻¹) and Sphaceloma ampelimum (EC₅₀ = 0.040 mg L⁻¹), even stronger than Boscalid, a new nicotinamide fungicide. Additionally, both compounds 1 and 2 showed strong activities against Plutella xylostella (90% and 80%, respectively, at 1000 mg L⁻¹).     

Structure and insecticidal activities of pyrethroids available through new methods of synthesis

Starting from derivatives of cyclobutanone the synthesis is described of α-cyano-3-phenoxybenzyl esters of 2,2-dimethylcyclopropanecarboxylic acid, substituted in the 3-position of the cyclopropane ring by an alkoxy, alkylthio, phenoxy or phenylthio group. The insecticidal activities of these synthetic pyrethroids towards adult Musca domestica, and larvae of Aedes aegypti, Spodoptera littoralis and Heliothis virescens are reported and compared with known pyrethroids.     

含吡唑-4-甲酰胺的嗜球果伞素类化合物的设计、合成及杀虫活性

为了发现新的农用高活性化合物,将具有杀螨活性的嗜球果伞素类化合物与具有杀菌活性的吡唑酰胺类化合物的活性亚结构进行拼接,设计并合成了16个新化合物,通过核磁共振氢谱、碳谱及高分辨质谱等手段表征了其结构。生物活性测试结果表明,目标化合物虽然没有预期的杀螨和杀菌活性,但是表现出了良好的杀虫活性,其中8个化合物在500 mg/L下对黏虫Mythimna separata的杀虫活性为100%。