Design, synthesis, insecticidal activity and structure-activity relationship of 3,3-dichloro-2-propenyloxy-containing phthalic acid diamide structures

BACKGROUND: Phthalic acid diamide derivatives are among the most important classes of synthetic insecticides. In this study, a 3,3‐dichloro‐2‐propenyloxy group, the essential active group of pyridalyl derivatives, was incorporated into phthalic acid diamide derivatives with the aim of combining the active groups to generate more potent insecticides. RESULTS: Thirty‐one new phthalic acid diamides were obtained, and these were characterised by ¹H and ¹³C NMR. The structure of N²‐[1,1‐dimethyl‐2‐(methoxy)ethyl]‐3‐iodo‐N¹‐[4‐(3,3‐dichloro‐2‐propenyloxy)‐3‐(trifluoromethyl)phenyl]‐1,2‐benzenedicarboxamide was determined by X‐ray diffraction crystallography. The insecticidal activities of the compounds against Plutella xylostella were evaluated. The title compounds exhibited excellent larvicidal activities against P. xylostella. Structure‐activity relationships revealed that varying the combination of aliphatic amide and aromatic amide moieties, or the nature and position of substituent Y on the aniline ring, could aid the design of structures with superior performance. CONCLUSION: A series of novel phthalic acid diamides containing a 3,3‐dichloro‐2‐propenyloxy group at the 4‐position of the aniline ring were designed and synthesised. Structure‐activity relationships with the parent structure provided information that could direct further investigation on structure modification. Copyright © 2012 Society of Chemical Industry     

新型七氟异丙基取代2,2-二氟-1,3-苯并二氧-5-乙酰胺衍生物的合成与杀虫活性

为探索环境友好新型农药先导化合物,通过水相中酰胺缩合反应合成了16个未见文献报道的七氟异丙基苯基取代的2,2-二氟-1,3-苯并二氧-5-乙酰胺类目标化合物。其结构通过核磁共振氢谱、氟谱以及高分辨质谱确认。初步生物活性测定表明,部分目标化合物对蚕豆蚜虫和粘虫表现出良好的杀虫活性,初步构效关系显示苯环上取代基的种类和位置在化合物的杀虫活性中起关键作用。     

嗜线虫致病杆菌对小菜蛾的致死和亚致死效应室内评价

嗜线虫致病杆菌是与昆虫病原线虫共生的细菌,对小菜蛾等多种害虫具有广谱的杀虫活性。为了深入了解该菌的杀虫活性,在室内测定了嗜线虫致病杆菌HB310 ( 简称 Xn HB310)菌株对小菜蛾幼虫的致死和亚致死效应以及持效期。结果表明, Xn HB310菌液对小菜蛾2龄和3龄幼虫72 h的LC50值分别是3.32×104 和8.56×104 CFU/mL,其活性组分主要存在于菌株细胞和经50 kDa超滤膜超滤后的上清液中。此外, Xn HB310菌液对小菜蛾幼虫还表现出明显的拒食活性,其2龄和3龄幼虫的拒食中浓度(AFC50)分别为4.03×105和8.48×105 CFU/mL。将2.24×106 CFU/mL菌液喷施到甘蓝苗上,其在室内的持效期为3~4 d。用亚致死剂量(LC30和LC50)的菌液饲喂小菜蛾2龄幼虫,存活幼虫的生长发育指标、蛹重、雌虫寿命以及成虫产卵量均明显下降,推测这可能导致小菜蛾下一代种群数量减少。研究结果表明,嗜线虫致病杆菌HB310菌株具有开发成为杀虫剂的潜力。     

Assessment of resistance risk in Spodoptera exigua (Hübner) (Lepidoptera: Noctuidae) to chlorantraniliprole

BACKGROUND: Beet armyworm, Spodoptera exigua (Hübner) (Lepidoptera: Noctuidae), is a major pest of numerous cultivated crops. Chlorantraniliprole, the first commercialised ryanodine receptor insecticide from the anthranilic diamide class, has exceptional insecticidal activity on a range of lepidopteran pests. The aim of this study was to assess the resistance of S. exigua to chlorantraniliprole in the laboratory. RESULTS: A field‐collected population of S. exigua was selected after repeated exposure to chlorantraniliprole to determine the risk of resistance evolution. After 22 generations of selection, there was a 12.0‐fold increase in LC₅₀. The realised heritability (h²) of resistance was estimated as 0.1082 by using threshold trait analysis. The projected rate of resistance evolution indicated that, if h² = 0.1082 and 70% of the population was killed at each generation, then a tenfold increase in LC₅₀ would be expected in 21.7 generations for chlorantraniliprole. CONCLUSION: These results show that the risk of resistance development to chlorantraniliprole exists in S. exigua after continuous application. Copyright © 2011 Society of Chemical Industry     

Insecticidal activity of chemical constituents from Aristolochia pubescens against Anticarsia gemmatalis larvae

Acetone and ethanol extracts of the tubercula and several compounds isolated from Aristolochia pubescens (Willd) were bioassayed on velvetbean caterpillars, Anticarsia gemmatalis (Hübner), for evaluation of the insecticidal activities. Of the extracts subjected to bioassay, the acetone extract showed the highest activity. (-)-Cubebin did not show activity against soybean caterpillars, whereas aristolochic acid and ent-kaur-15-en-17-ol increased the larval period. These compounds, and (+)-eudesmin and (+)-sesamin, reduced the viability of this period, giving rise to malformed adults. These extracts and compounds are therefore potential botanical insecticide agents for the control of velvetbean caterpillars in soybean crops.     

棉铃虫对常见化学农药的触角电位反应

利用电生理技术测定了棉铃虫对 15种常见农药的触角电位反应 (EAG) ,发现棉铃虫对不同农药品种的EAG反应差异很大 ,并且雌、雄蛾对某些农药品种的EAG反应截然不同 ,存在较大的性别差异。以上结果可为棉田害虫防治有选择地使用化学农药提供部分依据     

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%。     

含5-苯基2-呋喃环的3(2H)哒嗪酮类衍生物的合成与生物活性(I)(英文)

为探索新的农药先导化合物,经取代苯基呋喃甲酰氯与5-肼基-3(2H)哒嗪酮反应,得到15个未见文献报道的含呋喃环3(2H)哒嗪酮类化合物,其结构均通过了红外光谱、核磁共振氢谱和元素分析确认。初步生物活性测定结果表明,目标化合物具有良好的杀菌活性,但杀虫活性较弱。其中化合物3k在50 mg/L时对灰霉病菌的抑制率为86.29%±1.51%,与对照药剂腐霉利相当。初步的构效关系研究结果显示,苯环上取代基的种类和位置对杀菌活性有重要影响。     

Sites of Action of Noncompetitive GABA Antagonists in Houseflies and Rats: Three-Dimensional QSAR Analysis

Quantitative structure–activity relationships for insecticidal activity (against houseflies) and competitive activity against a specific [³⁵S]tert-butylbicyclophosphorothionate binding (to rat brain membranes) of some picrotoxinin-type 4-aminobutyric acid antagonists, including γ-BHC, endosulfan, bicyclophosphates, dioxatricyclododecenes and related compounds, were examined three-dimensionally using comparative molecular field analysis (CoMFA). The antagonists were classified into two series according to their molecular shapes: i.e. whether their structure was ‘linearly’ extended beyond the ‘mast-head’ position of the ‘boat-like’ skeletons (series 1) or not (series 2). The CoMFA showed that the slopes in steric and electrostatic fields around the molecule were significant for both series in governing the potency variations in insecticidal and binding activities. Hydrophobicity, a possible factor controlling transport behaviour of compounds, was significant in governing variations in insecticidal activity, but not for the case of the rat membrane binding. Assuming that there is a slight topological difference between series 1 and 2 compounds in terms of the mode of binding with the housefly receptor site, the insecticidal activity was analysable with a single equation for the combined set of compounds, but the rat membrane binding was not. The sterically and electrostatically favourable regions surrounding the molecular series indicated by CoMFA were roughly located at positions so as to interact with the binding subsites on the receptors proposed previously. © of SCI.     

Tachinid parasitoids (Diptera: Tachinidae) of<Emphasis Type="Italic">Spodoptera exigua</Emphasis> in cotton fields in Diyarbakır,Turkey

Tachinid parasitoidsExorista xanthaspis (Wiedemann),Nemorilla maculosa (Meigen),Palesisa maculosa (Villeneuve) andDrino imberbis (Wiedemann) were obtained fromSpodoptera exigua (Hübner) (Noctuidae) larvae collected from cotton fields in Turkey.S. exigua is a new host record forN. maculosa, andP. maculosa is recorded from Turkey for the first time. http://www.phytoparasitica.org posting July 14, 2004.     

Monitoring of stored tobacco insect pests by means of pheromones: the case ofEphestia elutella (Hübner) andLasioderma serricorne Fabricius in South Europe

Results obtained in the monitoring of stored tobacco pests by pheromones are reported. In GreeceEphestia elutella (Hübner) is likely to have at least 3 generations per year: the first one appears in early May, the second one during the last week of June and the third one— the most populated and the longer lasting—in August. In the same environmentsPlodia interpunctella (Hübner) has shown about 5 generations per year. The first on appeared in late May; the remaining 4—definitely overlapping—are placed in mid-June, in July, in early August and early September. In Italy four commercial pheromone dispensers effective in trappingLasioderma serricorne Fabricius have been compared. The results pointed out highly significant differences of the efficacy of the four different dispensers tested.L. serricorne was present in the tobacco store from June to October with a quite remarkable increase between August and early September.     

含七氟异丙基的3-酰氨基苯甲酰胺类化合物的合成及杀虫活性

设计合成了一系列新颖的含七氟异丙基的3-酰氨基苯甲酰胺类化合物,其结构均经核磁共振氢谱、质谱和高分辨质谱确证。初步生物活性测试结果表明,在20 mg/L下,部分化合物对小菜蛾Plutella xylostella具有较高的杀虫活性,其中 8j 在4 mg/L下对小菜蛾的致死率达100%。     

靶向乙酰胆碱酯酶和几丁质合成酶杀虫剂衍生化合物三维定量构效关系模型构建

为获得活性更佳且同时具备苯甲酰基脲类和氨基甲酸酯类活性的新型双靶标杀虫剂——N-氯磺基-N-甲基氨基甲酸酯衍生物,构建此类化合物的三维定量构效关系（three-dimensional quantitative structure-activity relationship,3D-QSAR）模型,以18种具有双靶标活性的N-氯磺基-N-甲基氨基甲酸酯衍生物为训练集,分别采用比较分子力场分析（comparative molecular field analysis,CoMFA）法和比较分子相似性指数分析（comparative molecular similarity index analysis,CoMSIA）法进行3D-QSAR模型的构建,基于3D-QSAR模型分析同一骨架取代基的变化带给化合物的活性变化,预测不同力场对化合物活性的影响,并对设计的衍生化合物进行活性预测分析。结果表明,经CoMFA法和CoMSIA法构建的3D-QSAR模型可信度高（交叉验证系数q²分别为0.728和0.563）,且有良好的活性预测能力（非交叉验证系数r²分别为0.954和0.981）。基于该模型得到的化合物预测活性与实际活性残差较小且存在良好的线性关系,进一步证明所得3D-QSAR模型的可靠性。通过分析3D-QSAR模型的力场分布,推测在R¹基团处引入位阻较大的疏水性基团、在R²基团苯环的邻位引入同时具有负电性和疏水性但不含卤素原子的基团、用负电性的大位阻基团取代R基团等均可提高N-氯磺基-N-甲基氨基甲酸酯的活性。基于此设计的20种衍生化合物的活性变化从正反两方面印证了该推测的合理性。研究成果可用于指导兼具苯甲酰基脲类和氨基甲酸酯类杀虫剂作用机制的N-氯磺基-N-甲基氨基甲酸酯衍生物的设计。     

Occurrence of Arthropods in a Central Italy feed-mill

This paper deals with the Arthropods fauna collected by bait and pheromone traps and categorized during one-year study in a Central Italy feed-mill. A total of 17,919 Arthropods were collected: Arachnida, Isopoda and Insecta. In the Arachnida we found mites, pseudoscorpions and mostly spiders; while in the Isopoda the only species noted wasPorcellio scaber (Latreille); in the Insecta 9 orders and 33 determined species were associated with the feed-mill: Collembola, Thysanura, Dermaptera, Psocoptera, Rhynchota, Lepidoptera, Coleoptera, Diptera and Hymenoptera. In the order Lepidoptera about 55% of the insects were collected. Eight species of stored product Lepidoptera were cuaght:Ephestia kuehniella. Zeller, was the most abundant and wide-spread in the feed-mill (with 8,230 males, 83.53% of Lepidoptera trapped) followed byPlodia interpunctella (Hübner), (1,415 males) andEphestia elutella, (Hübner), (161 males). Coleopterans made up 40.43% of the insects collected.Tribolium confusum J. Du Val, was the most abundant and widespread in the feed-mill (with 5,451 specimens, 75.23% of Coleoptera trapped); less abundant wereOryzaephilus surinamensis (L.) (752 specimens),Tribolium castaneum (Herbst) (359 specimens),Attagenus brunneus Fald. (223 specimens),Stegobium paniceum (L.) (156 specimens) andSitophilus oryzae (L.) (118 specimens). Arthropods infestation level found during this survey were probably directly proportional to the amount of debris present in the departments. Because of these and other peculiarities, the feed-mill staff have to be continually alert to prevent, detect, and control pest problems within their work environment.     

On the species ofRhyacionia Hübner [1825] (Lepidoptera: Tortricidae) in Turkey

Three forest pest species of the genusRhyacionia Hübner [1825] (Lepidoptera: Tortricidae) that are known to damagePinus species are found in Turkey:R. buoliana ([Denis & Schiffermüller], 1775),R. pinicolana, (Doubleday, 1849) andR. pinivorana (Lienig & Zeller, 1846).R. pinivorana is recorded for the first time from Turkey.R. pinicolana, first recorded in 1999, is now reported for the second time from Turkey. Photographs are presented of adult males and their genitalia of all taxa and the species distribution is shown on a map.     

Synthesis and bioactivity evaluation of novel spiromesifen derivatives

BACKGROUND: The development of environmentally friendly and novel structural pesticides is now an area of intense research in the agriculture field. Spirocyclic tetronic acids such as spiromesifen are typical compounds of this kind. In order to discover novel compounds with improved and broader-spectrum insecticidal activities, a series of spiromesifen derivatives were synthesised and bioassayed. RESULTS: The derivatives were identified by ¹H NMR and MS. Preliminary bioassays demonstrated that some bioactivities of compounds 5a to 5u were better and had a broader spectrum than the lead compound spiromesifen. Moreover, these compounds showed better insecticidal activities against Mythimna sepatara and Aphis fabae than acaricidal activities against Tetranychus cinnabari. Furthermore, LC₅₀ of 5s against Aphis fabae reached 1.09 mg L⁻¹. At the same time, compounds 5g, 5i, 5k and 5r also warrant further study because of their superior bioactivities to spiromesifen. What is more, suitable carbon chain length in the 4-position ester and the log P value of these spiromesifen derivatives dramatically influenced their insecticidal activities. Butyric or pentanoic ester and a log P value of 4.0–6.0 may be preferred. CONCLUSION: The present work demonstrates that some spiromesifen derivatives can be used as potential lead compounds for developing novel insecticides and acaricides. Copyright © 2011 Society of Chemical Industry     

甲氨基阿维菌素苯甲酸盐微乳剂对蔬菜害虫的控制作用

0.5%甲氨基阿维菌素苯甲酸盐微乳剂以药量10 mL/667 m²防治甜菜夜蛾的效果明显优于其2倍使用剂量的乳油,药后3～7 d,对苋菜上甜菜夜蛾的防治效果达到85%以上,显著优于1.8%阿维菌素乳油33.33 mL/667 m²防治效果;施药量8.33 mL/667 m²,药后7 d,对丝瓜上美洲斑潜蝇的防治效果达85%以上,与1.8%阿维菌素乳油50 mL/667 m²防治效果差异不显著。     

Evaluation of a wettable powder formulation for the nuclear polyhedrosis virus of Anticarsia gemmatalis (Lep.: Noctuidae)

The influence of different carriers on the physical and biological stability of Baculovirus anticarsia wettable powder formulations was studied. The formulations were obtained by mixing the purified polyhedra of B. anticarsia with a carrier and drying the suspension in a bench spray dryer. Bioassays with Anticarsia gemmatalis Hübner showed that activity was maintained with the amorphous silica, attapulgite and kaolinite after a year of storage. In the presence of bentonite, activity declined 50% in the same period. All formulations, except kaolinite, maintained the physical parameters required of a good wettable powder. Kaolinite formulation showed reduction in wettability and particle agglomeration in storage. © 1997 SCI     

八种十字花科寄主植物真叶和子叶的化学成分及其对小菜蛾生长发育及生理代谢的影响

为明确小菜蛾Plutella xylostella对寄主植物真叶和子叶的适合度,于室内测定8种十字花科植物改良青杂3号、改良露头青、陕油0913、甘杂1号、超级火箕青、四月慢、绿球66和中花尖叶芥蓝真叶和子叶的营养物质和次生代谢物质的含量,并测定取食后小菜蛾幼虫的取食选择性、发育历期、蛹重、保护酶和解毒酶活性。结果显示,8种寄主植物真叶的可溶性糖、总氨基酸、单宁、类黄酮和总酚含量之间差异显著,且大部分均显著高于其子叶,8种寄主植物子叶的可溶性糖、总氨基酸、单宁、类黄酮和总酚含量之间也差异显著。小菜蛾3龄幼虫偏好取食真叶;取食8种寄主植物真叶后成虫前期的发育历期为12.3～16.3 d,取食子叶后成虫前期的发育历期为14.3～18.6 d;取食子叶的蛹重明显低于取食其真叶;取食8种寄主植物真叶的小菜蛾幼虫体内超氧化物歧化酶（superoxide dismutase,SOD）、过氧化物酶（peroxidase,POD）、过氧化氢酶（catalase,CAT）、谷胱甘肽S-转移酶（glutathione S-transferase,GST）、羧酸酯酶（carboxylesterase,Car...     

Optimization of production of nucleopolyhedrovirus ofHelicoverpa armigera throughout larval stages

Studies were carried out to optimize production of nucleopolyhedrovirus of American bollworm,Helicoverpa armigera (Hübner), by treating larvae individually with an inoculum dose that allowed maximal larval growth and also gave the highest occlusion bodies (OB) yield/larva. The maximum virus yield of 12.2x 10⁹ OB/larva was obtained when 6-day-old larvae were fed individually with a dose of 1 x 10³ OB. Topical spiracular treatment of larvae as old as 8 days with 10 μ of 2x 10⁷ OB ml^-1 gave the highest yield, of 15.2x 10⁹ OB from 13-day-old larvae, of 12.8x 10⁸ OB from prepupae and of 1.49x 10⁸ OB from pupae at the time of their death. These studies showed that dietary inoculum is the best route for 6-day-old larvae and topical spiracular treatment is the best for 8-day-old larvae.