Synthesis and insecticidal evaluation of imidacloprid analogs

Imidacloprid analogues containing a nitroalkylidene instead of a nitroguanidine unit have been prepared and evaluated for investigation as potential insecticides. No nitroalkylidene analogue showed significant activity against the test insects. © 1998 Society of Chemical Industry     

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。     

二氢吡唑邻甲酰氨基苯甲酰胺衍生物的合成及杀虫活性

以邻氨基苯甲酸和4,5-二氢吡唑-5-甲酸为原料,制备得到苯并噁嗪酮,所得产物与取代胺作用制得8个结构新颖的二氢吡唑邻甲酰胺基苯甲酰胺类化合物,其结构用核磁共振氢谱和质谱进行了表征。生物活性试验结果表明,在500 mg/L质量浓度下,部分化合物对小菜蛾Plutella xylostella、苜蓿蚜Aphis medicaginis和稻飞虱Nilaparvata lugens的致死率达100%。     

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     

含三氟甲基异噁唑啉类化合物的合成及杀虫活性

以取代α-三氟甲基苯乙烯和取代的肉桂醛肟为原料,经过1,3-偶极环加成反应,合成了16个未见文献报道的含三氟甲基异噁唑啉结构的目标化合物,其结构经1H NMR和LC-MS确认。初步杀虫活性测试结果表明:在500 mg/L下,大部分目标化合物对斜纹夜蛾Prodenia litura和粘虫Mythimna sepatara具有一定的杀虫活性,其中ZJ11对粘虫的致死率达100%,即使在100 mg/L下,其致死率仍达80%。     

Synthesis and insecticidal activity of new pyrethroids

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D ‐mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)‐3‐formyl‐2,2‐dimethylcyclopropane‐1‐carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D ‐mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)‐3‐[(Z)‐2‐(4‐chlorophenyl)vinyl]‐2,2‐dimethylcyclopropane‐1‐carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana. Copyright © 2009 Society of Chemical Industry     

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。     

The synthesis and insecticidal activity of indole-derived carbamates

Thirty-seven novel 3H-indolyl and indolinyl carbamates were synthesised as potential insecticides. They were generally found to be good inhibitors of acetylcholinesterase in vitro, but although several compounds were highly insecticidal no correlation was found between their in vitro activity and their in vivo performance. Experimental evidence suggested that the insecticidal activity of the compounds was governed by a combination of their relative rates of penetration into insects and subsequent metabolic breakdown.     

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。     

细交链孢菌酮酸及其衍生物的合成与杀虫活性

为了寻找具有较高杀虫活性的特胺酸化合物,以天然活性产物细交链孢菌酮酸(TeA)作为先导化合物,利用酰基化米氏酸作为酰基化试剂,设计、合成了26个3-位不同酰基取代和5-位不同取代的含特胺酸骨架衍生物 4a~4s、5a~5g、7a 和 8a ,其中14个化合物未见文献报道,所有目标化合物的结构均经核磁共振氢谱、碳谱和高分辨质谱确证。初步杀虫活性测定结果表明,在100 μg/mL下处理72 h内,所有目标化合物对麦长管蚜Macrosiphum avenae (Fabricius)均表现出良好的杀虫活性,并具有内吸性,其中化合物 5d 和 7a 48 h致死率为100%,高于对照药剂螺虫乙酯,具有作为先导化合物进一步研究的价值。对处理后的小麦植株进行残留量测定,结果表明目标化合物 4e、5c、7a 和 8a 能被植株较好的吸收 。 该研究结果可为进一步研究具有特胺酸骨架化合物的构效关系提供参考。     

A new pyrethroid of high insecticidal activity

New pyrethroids containing heterocyclic rings in the alcohol moieties were synthesised and their insecticidal activities were studied. Of these new pyrethroids, 3-benzylpyrrol-1-ylmethyl (1RS-cis, trans-3(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate was found to be the most effective, having higher activity than permethrin against Musca domestica by a topical application method. In addition, para-substituted analogues of the 3-benzylpyrrol-1-ylmethyl ester were also synthesised to study the substituent effects on insecticidal activities; the residual effects of these compounds against Blattella germanica were also examined.     

The synthesis of pyrroles with insecticidal activity

The 2-aryl-4-bromo-5-trifluoromethylpyrrole-3-carbonitriles represent a new class of insect control agents. The high insectidical activity observed in this series prompted us to investigate the preparation of regioisomeric arylhalotrifluoromethylpyrrole carbonitriles. The synthesis and biological activity of eight of the twelve possible regioisomers are described and discussed.     

含嘧啶氧基和一氟甲氧基的吡唑邻甲酰氨基苯甲酰胺的合成及杀虫活性

以取代邻氨基苯甲酸和取代吡啶基吡唑羧酸为原料,合成了10个结构新颖的含嘧啶基和一氟甲氧基的吡唑邻甲酰氨基苯甲酰胺类化合物,其结构通过1H NMR和MS表征。盆栽法试验表明,在500 mg/L 质量浓度下,部分化合物对小菜蛾 Plutella xylostella 和苜蓿蚜 Aphis medicaginis的相对防效达100%。     

Structural modifications increase the insecticidal activity of ryanodine

The toxicity of ryanodine ( 1 ) and 9,21-didehydroryanodine ( 2 ) (the principal active ingredients of the botanical insecticide ryania) to adult female house flies (Musca domestica L.) is attributable to binding to the ryanodine receptor (ryr) and thereby disrupting the Ca²⁺-release channel. These ryanoids, assayed in house flies with piperonyl butoxide (PBO) to suppress cytochrome P450-dependent detoxification, give injected KD₅₀ values of 0·07–0·11 μg g^-1, injected LD₅₀ values of 0·39–0·45 μg g^-1 and topical LD₅₀ values of 12– 50 μg g^-1. They inhibit the [³H]ryanodine binding site of house fly and rabbit muscle with IC₅₀ values of 3–10 nM . This study examines the effect of structure on potency, with 15 variants of the cyclohexane substituents, two 4,6-cyclic boron and two methylated derivatives, and four modifications of the isopropyl and ester substituents. The most effective compound examined was 10-deoxy- 2 ( 3 ) which was more potent than 2 by 2–4-fold on injection and 29-fold applied topically following PBO (LD₅₀ 0·41 μg g^-1). Additional high-potency compounds were 10-oxo- 1 and the cyclohexane variants with lactam, 21-nor-9-oxo and 21-nor-10-deoxy substituents. Other modifications usually reduced toxicity. The injected knockdown potency of the ester ryanoids was generally related to their effectiveness in competing with [³H]ryanodine at the ryr of rabbit skeletal muscle. Two non-ester ryanoids, ryanodol and 9,21-didehydroryanodol, were found to be more toxic than predicted from their potency at the ryr and may therefore act in a different manner such as at a K⁺ channel, as suggested by Usherwood and Vais. Clearly ryanoids are challenging prototypes for a potential new generation of insecticides. © 1997 SCI.     

Synthesis and insecticidal activity of new amide derivatives of piperine

The natural lipophilic amides piperine and piperiline were isolated from Piper nigrum L (Piperaceae). Piperine was hydrolysed into piperic acid (85% yield) which was converted into 16 amides (28–89% yield). The contact toxicity of all synthetic amides, and also that of piperine and piperiline, at the dose 10 µg per insect, was evaluated for the Brazilian economically important insects Ascia monuste orseis Latr, Acanthoscelides obtectus Say, Brevicoryne brassicae L, Protopolybia exigua DeSaus and Cornitermes cumulans Kollar. The results demontrated that the insects have different sensivities to the various amides, with mortality ranging from 0 to 97.5% according to the compound and insect species. © 2000 Society of Chemical Industry     

禾本科植物的杀虫及抑菌活性研究进展

禾本科植物活性多样。本文综述了禾本科香茅属(Cymbopogon)、芦竹属(Arund)、燕麦属(Avena)、蜈蚣草属(Eremochloa)、臂形草属(Brachiaria)、白茅属(Imperata)、高粱属(Sorghum)、香根草属(Vetiveria)和玉蜀黍属(Zea)等9个属的杀虫和抑菌活性植物及其活性成分。     

含1,4-二氢吡啶环的新烟碱类化合物的合成及杀虫活性

通过NTN32692、芳香醛和氰基乙酸乙酯参与的多组份反应合成了15个全新的含1,4-二氢吡啶环的新烟碱类化合物,其结构均经过核磁共振氢谱、高分辨质谱、红外光谱确证。室内生物测定结果表明,目标化合物对孑孓Culex pipiens pallens、粘虫Pseudaletia separate Walker和蚜虫Aphis craccivora具有较高的杀虫活性,部分化合物在质量浓度为500 mg/L下对粘虫和蚜虫的致死率可达到100%。