新型邻胺基苯甲酰胺类杀虫剂的创制研究

自主设计、合成了系列新型邻胺基苯甲酰胺类化合物,并对其进行了杀虫活性、安全性、毒性、工艺、制剂、温室和/或田间防治效果等研究,获得了Ia、Ib和Ic等系列自主知识产权的高杀虫活性化合物.结果 表明化合物Ic等对咀嚼口器害虫如粘虫和小菜蛾等的活性较邻胺基苯甲酰胺类杀虫剂氯虫苯甲酰胺水平相当或更胜一筹,对刺吸口器害虫如蚜虫等的活性远优于氯虫苯甲酰胺及溴氰虫酰胺.田间药效试验进一步证实,Ic等对咀嚼口器害虫如水稻二化螟、稻纵卷叶螟、甜菜夜蛾等的防治效果相当于或优于氯虫苯甲酰胺,对刺吸口器害虫如蚜虫等的防治效果优于溴氰虫酰胺.新型邻胺基苯甲酰胺类化合物Ic等可作为候选杀虫剂进一步研究开发.     

新型邻甲酰氨基苯甲酰胺类农药氯虫酰胺的研究概述

邻甲酰氨基苯甲酰胺类化合物是最近发现的一类高效、低毒和作用机制独特的新型杀虫剂。本文对邻甲酰氨基苯甲酰胺类杀虫剂的发现过程及其第一个商品化潜在鱼尼丁受体激活剂品种氯虫酰胺的合成、生物学、毒理学和作用机理等方面的研究情况作一概述。     

双酰胺类杀虫剂的开发沿革

近年上市的双酰胺类是作用于鱼尼汀受体的新颖杀虫剂类别。由于其具有诸多特点,颇受国内外研究人员的青睐,并被广泛地研究开发。介绍了国内外对双酰胺类的邻苯二酰胺和邻甲酰胺基苯甲酰胺的发现和开发过程以及作用机制。     

邻甲酰氨基苯甲酰胺类农药研究概述

邻甲酰胺基苯甲酰胺类杀虫剂具有高效、低毒和作用机制独特等特点,是目前最具发展潜力的杀虫活性化合物。笔者结合第一个商品化的邻甲酰胺基苯甲酰胺类杀虫剂氯虫酰胺对邻甲酰胺基苯甲酰胺类杀虫剂的发现、合成、生物学、毒理学、作用机理和生态安全等方面的研究情况做一概述。     

新型邻甲酰氨基苯甲酰胺类杀虫剂环溴虫酰胺及其开发应用

新型邻甲酰氨基苯甲酰胺类杀虫剂环溴虫酰胺具有与氯虫苯甲酰胺相似的化学结构和相同的杀虫机理。通过变构调节鱼尼丁受体,环溴虫酰胺对鳞翅目、双翅目和鞘翅目等多类害虫表现出了高杀虫活性,同时对哺乳动物、有益节肢动物和环境的影响较小。环溴虫酰胺的杀虫谱广、用量低、不感温、持效期长,可作为氯虫苯甲酰胺的重要补充。环溴虫酰胺可共用氯虫苯甲酰胺和溴氰虫酰胺的关键中间体进行生产,再制成单剂或复配,单用或与多种杀虫杀菌剂混合使用,一次施用即可同时控制水果、蔬菜、玉米、茶树和草坪等作物上的多种害虫。环溴虫酰胺的市场潜力较大,其开发应用情况值得关注。     

新型邻甲酰氨基苯甲酰胺类杀虫剂的研究进展

介绍了新型邻甲酰氨基苯甲酰胺类杀虫剂的研究进展。根据具体化学结构类型不同分为五大类，概述了具有较好生物活性的化合物，介绍了氯虫酰胺的创制经纬和合成方法。     

二酰胺结构鱼尼丁受体杀虫剂的研究进展

二酰胺类鱼尼丁受体杀虫剂因结构新颖、作用机理独特、杀虫活性高而受到广泛的关注。本文介绍了2007年以来国内外在二酰胺类邻苯二甲酰胺类和邻甲酰氨基苯甲酰胺类鱼尼丁受体杀虫剂方面的最新研究进展。     

噻虫酰胺对5种鳞翅目昆虫的杀虫活性研究

噻虫酰胺,试验代号JS9117,是江苏省农药研究所股份有限公司于2009年创制发现的新型邻杂环苯甲酰胺类化合物。以氯虫苯甲酰胺为对照药剂,采用浸叶碟饲喂法、浸虫法及综合法等处理小菜蛾、甜菜夜蛾、斜纹夜蛾、棉铃虫、二化螟等幼虫,研究了噻虫酰胺的杀虫活性。结果表明,噻虫酰胺对5种鳞翅目昆虫具有高活性,对小菜蛾的活性是氯虫苯甲酰胺的1.58～1.83倍,对甜菜夜蛾是0.64～4.87倍,对斜纹夜蛾是1.04～1.34倍,对棉铃虫是1.36～1.98倍,对二化螟是0.23～1.33倍。本研究为噻虫酰胺的进一步研发和应用提供了参考。     

邻氨基苯甲酰甲基异(硫)脲类衍生物的合成与杀虫活性初步研究

以杀虫剂氯虫苯甲酰胺为先导,设计并合成了8个邻氨基苯甲酰甲基异(硫)脲类化合物。目标化合物的结构经核磁表征确认。初步生物活性测试结果表明,此类化合物对小菜蛾具有较好的杀虫活性。     

新型邻甲酰氨基苯甲酰胺类化合物的研究进展

邻甲酰氨基苯甲酰胺类杀虫剂具有作用机制独特、高效、低毒等特点,是目前市场等最具发展潜力与前景的杀虫活性化合物。从结构划分的角度对新型邻甲酰氨基苯甲酰胺类化合物及其杀虫活性研究情况做了简要综述,展望了其发展前景。     

丙烯海松酸基双酰胺类化合物的合成及生物活性研究

经松香与丙烯酸的D-A加成反应制备丙烯酸改性松香,从中分离提纯得到丙烯海松酸。将丙烯海松酸转化为双酰氯,再与苯胺类化合物发生N-酰化反应,合成得到一系列新型丙烯海松酸基双酰胺类化合物,利用IR、1HNMR和13 CNMR表征了目标化合物的结构。初步生物活性测试表明,所合成的目标化合物在50μg/mL浓度下都对苹果轮纹病菌有一定的抑制活性,化合物丙烯海松酸基双对甲氧基苯酰胺在100μg/mL浓度下对油菜的胚根生长显示良好的抑制活性(达到A级活性水平)。     

新型邻甲酰胺基苯甲酰胺衍生物的合成与生物活性研究

合成了9个新型邻甲酰胺基苯甲酰胺衍生物,其结构经1H NMR进行确证。初步杀虫、杀螨活性测试表明所合成的化合物在1 000 mg/L浓度下对磷翅目的粘虫(Mythimna separata)有100%的致死率。在500 mg/L浓度下,大多化合物对同翅目的蚕豆蚜(Aphis fabae)以及稻黑尾叶蝉(Nephotettix cincticeps)具有明显活性,如化合物3-溴-1-(3-氯-2-吡啶基)-N-[4-氯-2-甲基-6-[((3,3-二氯烯丙氧基)氨基)羰基]苯基]-1H-吡唑-5-甲酰胺(14c)对蚕豆蚜的致死率达到89.29%;化合物14b对叶蝉的致死率达到81.82%。在500 mg/L浓度下,所合成化合物对蜱螨目棉红蜘蛛(Tetranchus urticae)没有表现出明显活性。     

含N-(2-呋喃基)甲基的双酰胺类化合物合成及生物活性

将N-(2-呋喃基)甲基和氟代烷氧基引入双酰胺分子结构中,合成了4个新化合物。目标化合物均通过核磁共振氢谱、质谱、元素分析等表征。目标化合物对小菜蛾的活性与氯虫苯甲酰胺相当,对二化螟的持效作用明显好于已知化合物KC1和KC2。     

苯基膦酰二胺的合成

研究了以苯基膦酰二氯、氯气为原料合成苯基膦酰二胺。讨论了氨化反应的影响因素,优化的反应条件为:反应温度-25~-20℃,反应溶剂为无水乙醚,氨气流速为0.6 L/min,产品收率大于90%。该合成过程具有操作简单、反应条件温和、工艺过程易实现等特点。     

大环多酰胺的合成进展

本文综述了近年来发展的合成大环四酰胺的方法,与先形成二酰胺二羧酸的衍生物再进行环化或者直接进行环化相比,先形成二酰胺二胺这种中间体,再进行环化的分步合成方法是一种较有效的途径。     

Chimeric Investigations into the Diamide Binding Site on the Lepidopteran Ryanodine Receptor

Alterations to amino acid residues G4946 and I4790, associated with resistance to diamide insecticides, suggests a location of diamide interaction within the pVSD voltage sensor-like domain of the insect ryanodine receptor (RyR). To further delineate the interaction site(s), targeted alterations were made within the same pVSD region on the diamondback moth (Plutella xylostella) RyR channel. The editing of five amino acid positions to match those found in the diamide insensitive skeletal RyR1 of humans (hRyR1) in order to generate a human–Plutella chimeric construct showed that these alterations strongly reduce diamide efficacy when introduced in combination but cause only minor reductions when introduced individually. It is concluded that the sites of diamide interaction on insect RyRs lie proximal to the voltage sensor-like domain of the RyR and that the main site of interaction is at residues K4700, Y4701, I4790 and S4919 in the S1 to S4 transmembrane domains.     

Strukturvariationen durch Reaktionen der Thiocarbonylgruppe

Structural Variations by Reactions of the Thiocarbonyl Group The 2,3‐dihydrothiazol‐2‐thiones 1a—c have been methylated to the 2‐methylsulfanylthiazolium iodides 2a—c , which could be reacted with double activated CH‐acidic compounds like 4‐nitrophenylacetonitrile ( 3 ) to yield 5 and 6a,b , with malonic acid derivatives 7a—c to yield the push pull substituted ketene‐S,N‐acetales 8a—c or with 3‐aminorhoda‐nine derivatives to yield 12a,b . Vinylogous CH‐acidic compounds like 9a—d reacted with 2b to the push‐pull substituted butadienes 10a—d . With p‐phenethidine 2b formed depending on the reaction conditions either the rare structure of an ortho‐dithiocarbonic diester diamide ( 14 ) or the isothiourea 15 . With hydrazino compounds, 16a—c with hydrazono partial structure resulted. Efforts to acylate the unsubstituted nitrogen of 17 with carbonic acid ester derivatives always yielded the S‐acylated products 18 and 20a,b .     

3种双酰胺类杀虫剂防治甘蓝甜菜夜蛾的防效评价

[目的]筛选甘蓝甜菜夜蛾防治药剂氯虫苯甲酰胺的替代产品。[方法]每种药剂采取登记用量上下限作为试验剂量,用喷洒药剂悬浮液的方法进行田间试验。[结果]施药后3 d,10%四氯虫酰胺悬浮剂60 g a.i./hm2防效97.87%,200 g/L四唑虫酰胺悬浮剂30 g a.i./hm2防效96.11%,5%氯虫苯甲酰胺悬浮剂33.75 g a.i./hm2防效95.30%;药后15 d 10%四氯虫酰胺悬浮剂60 g a.i./hm2防效89.86%,200 g/L四唑虫酰胺悬浮剂30 g a.i./hm2防效88.07%,5%氯虫苯甲酰胺悬浮剂33.75 g a.i./hm2防效80.81%。[结论] 3种双酰胺类杀虫剂防治甘蓝甜菜夜蛾对作物安全,在氯虫苯甲酰胺抗性较强的地区,建议选择四氯虫酰胺和四唑虫酰胺作为替代产品。     

Synthesis and characterization of di‐polyester diamides

A series of di‐polyester diamides was synthesized via a nucleophilic ring opening polymerization process. FTIR investigations revealed the spectral characteristics evidencing the newly formed chemical bonds as well as the changes in the relative intensity of the characteristic peaks, due to the increasing side‐block lengths of the different members of the series. ¹H‐NMR analysis of the described materials confirmed the chemical structures seen by FTIR analysis. The side segment length of the different di‐polyester diamides was calculated from the integration ratios in the NMR spectra. The molecular weight results exhibited relatively small deviations from the stoichiometrically calculated values. All the members of the triblock series, with side blocks of up to 120 lactoyl units, were essentially amorphous and glassy at room temperature. The presence of two separate glass transitions indicated a segmented and microphase separated morphology. It was deducted that the amorphous nature of the relatively long poly(lactic acid) side blocks occurs due to the dominance of the hydrogen‐bonded central segment. Synthesis of a di‐polyester diamide containing a reduced number of hydrogen‐bond‐forming groups in the central segment yielded a partial side‐block crystallization. The di‐polyester diamide with 120 lactoyl unit‐long side blocks was eventually able to crystallize in solid state, following thermal treatment during thermal analysis. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of organic–inorganic adduct of dinaphtosulfide macrocyclic diamide and silicotungstic acid: study of interaction in solid and solution phase

An adduct compound containing dinaphtosulfide macrocyclic diamide and silicotungstic acid was prepared and characterized by elemental analyses, IR, UV–VIS spectrophotometry and diffuse reflectance spectrometry. The stoichiometry and stability of adduct were studied by conductometry in nitrobenzene (NB) solvent. This is the first report of the interaction of crown ether containing sulfur heteroatom and heteropoly acid. The interaction of the adduct compound with Hg²⁺ was studied by spectrophotometric and pH-metric methods in NB solvent. The formation constant of the Hg²⁺-adduct complex was calculated from the computer fitting of the obtained data. The extraction of Hg²⁺ and Pb²⁺ was studied from aqueous solution using this adduct compound.