米尔贝霉素类似物的合成及杀螨杀蚜活性

为寻找高活性的米尔贝霉素衍生物,以伊维菌素为原料,经脱糖、羟基保护、氧化、还原胺化、脱保护等将其转变为13-氨基米尔贝霉素类似物,通过三组分反应设计合成了一系列米尔贝霉素磺酰脒类化合物(7a~7i),并初步测定了其对朱砂叶螨Tetranychus cinnabarinus和豆蚜Aphis craccivora的室内活性。结果表明:各衍生物对朱砂叶螨和豆蚜均有较好的触杀活性,其中7f、7h和7i对朱砂叶螨24 h的LC50值分别为1.04×10–2、9.60×10–4和1.44×10–2 mg/L;7i对豆蚜24 h的LC50值为7.81 mg/L。米尔贝霉素13位氨基上磺酰化的结构修饰有助于提高米尔贝霉素类化合物的杀螨、杀蚜活性。     

天维菌素酰化衍生物的合成及杀虫杀螨活性

以天维菌素B、天维菌素B单糖苷和天维菌素B苷元为原料,经选择性C-5羟基保护,在C-13、C-4′和C-4″位引入不同酰基基团,合成了3个系列共23个天维菌素B酰化衍生物,并通过1H NMR、13C NMR和高分辨质谱对所有目标化合物的结构进行了表征。生物活性测定结果表明,所有衍生物对小菜蛾Plutella xylostella、朱砂叶螨Tetranychus cinnabarinus以及松材线虫Bursaphelenchus xylophilus均表现出不同程度的毒杀活性,其中天维菌素B C-4″位衍生物的活性优于C-4′位衍生物及13位衍生物。化合物8e对小菜蛾和松材线虫的毒杀活性最优,LC50值分别为9.2 mg/L和0.42 mg/L,化合物8b对朱砂叶螨的毒性最高,LC50值为0.0019 mg/L,均优于对照药天维菌素B。     

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     

Synthesis and insecticidal activities of novel derivatives of podophyllotoxin: Part XII

In order to find the biorational pesticides, eight novel 4β-substituted phenoxyaniline derivatives of podophyllotoxin have been synthesized with significant stereoselectivity and improved yields by employing the BF₃·Et₂O/NaI reagent system and evaluated for their antifeedant effect against 5th instar larvae of Pieris rapae and effect on the development of 5th instar larvae of P. rapae as well as for insecticidal activity against P. rapae. The antifeedant activities showed that these compounds exhibited less potent than podophyllotoxin. Though these derivatives showed less potent antifeedant activities than podophyllotoxin, they acted as growth development inhibitor to 5th instar larvae of P. rapae, which were found that the animals treated with podophyllotoxin and its derivatives showed moulting disturbances and/or deformities. Also, the insecticidal activity results show that all of these derivatives of PPT showed delayed insecticidal activity, which differs from traditional neurotoxic insecticides. Among them, compounds possessing a 4β-phenoxyaniline moiety substituted (CO₂C₂H₅, Cl and OH) at para position exhibited greater insecticidal activity against P. rapae than podophyllotoxin.     

含单氟甲氧基的双酰胺类化合物的合成及杀虫活性

以2,3-二氯吡啶为起始原料,经肼基化、环合、氧化、取代、水解、环合和胺解反应,合成了15个文献未见报道的新型含单氟甲氧基的吡唑邻甲酰氨基苯甲酰胺类化合物,其结构通过核磁共振氢谱和高分辨质谱确认。初步的杀虫活性测试结果显示,所有目标化合物在100 mg/L下对粘虫Oriental armyworm的致死率均为100%,当测试浓度降低至4 mg/L时,化合物 8a 、 8d 、 8g 、 8k 和 8n 的致死率仍为100%,值得进一步研究。     

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。     

吡啶联三唑类衍生物的合成及杀虫活性

以3-氨基-2-氯吡啶(1)为起始原料,经重氮化、叠氮化、环合和酰氯化反应,生成1-(2-氯吡啶-3-基)-5-甲基-1H-1,2,3-三唑-4-甲酰氯(5),(5)与取代苯胺反应,制得13个未见文献报道的吡啶联三唑类化合物,其结构通过 1H NMR和LC-MS表征。初步生物活性测定结果表明:在500 mg/L质量浓度下,所有目标化合物对粘虫 Mythimna separate 均有一定的杀虫活性,部分化合物致死率达100%;但在100 mg/L下,除化合物ZJ-7的致死率仍达100%外,其余化合物的活性明显降低,甚至无活性。     

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。     

Synthesis and insecticidal activities of pyridine ring derivatives of podophyllotoxin

In an attempt to find the biorational pesticides, we synthesized 12 pyridinyl derivatives of podophyllotoxin (PPT) and 4′-demthylepipodophylltoxin (4′-DMEP) in this study. Their structures and the α/β substitution at C-4 were confirmed by ¹H NMR, IR, MS spectral analyses and elemental analysis. The insecticidal activities were tested against fifth-instar larvae of Pieris rapae and the third-instar larvae of Cullex pipiens pallens at concentrations of 250 and 10 μg ml⁻¹. Four derivatives of PPT, 4.1, 4.2, 4.3 and 4.5, showed higher insecticidal activities against P. rapae than PPT, while three derivatives of PPT, 4.4, 4.5 and 4.6, displayed higher mosquito larvicidal activity than PPT, with LC₅₀ values of 1.66, 3.96 and 1.54 mg l⁻¹, respectively. Interestingly, we also found that the pyridine ring derivatives of PPT showed delayed insecticidal activity, which is different from traditional neurotic insecticides. The results suggest that 4′-OCH₃ in the PPT derivatives is essential to keep the insecticidal activity and the insecticidal activities of pyridine ring derivatives of PPT are higher than that of the derivatives of 4′-DMEP, supporting PPT has the potential to be a lead structure of semi-synthetic insecticides.     

Synthesis and insecticidal activities of novel oxime ether pyrethroids

A series of novel 2-methylthio-3'/4'-substituted acetophenone oxime O-ethers were synthesized by the reaction of the corresponding acetophenone oximes with halides of pyrethroid alcohols in the presence of sodium hydroxide and phase-transfer catalysis or with triethyl quaternary ammonium salts of halides of pyrethroid alcohols in the presence of sodium hydroxide. These compounds showed notable insecticidal activity against Homopteran and Lepidopteran pests. 2-Methylthio-4'-fluoroacetophenone oxime O-[(2-methylbiphenyl-3-yl)methyl] ether was more effective than the commercial insecticides chlorfenapyr and fenvalerate.     

Synthesis and insecticidal evaluation of N-substituted 2-nitroiminoimidazolidines

N-substituted and N,N′-disubstituted 2-nitroiminoimidazolidines were prepared from 2-nitroiminoimidazoline. The feeding-contact and systemic activities as insecticides of some of these new compounds have been evaluated. © 1998 Society of Chemical Industry     

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     

嘌呤氧基苯氧丙酸酯的合成及除草活性

以4,6-二氯-5-硝基嘧啶为起始原料,经过还原胺化、取代、醚化等一系列反应,得到11个未见文献报道的嘌呤氧基苯氧丙酸酯类化合物1a~1k,其结构经1H NM R和M S确认。初步生物活性测定表明:在200 mg/L下,所有目标化合物均表现出一定的除草活性,其中化合物1f((R)-2-(4-((9-(4-氯苯)-8-(三氟甲基-9H-嘌呤-6-基)氧)苯氧)丙酸丁酯)和1h((R)-2-(4-((9-(4-氯苯)-8-(三氟甲基-9H-嘌呤-6-基)氧)苯氧)丙酸乙酯)对靶标的抑制率几乎都达到100%。     

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     

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。     

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