Attract-and-kill strategy. Laboratory studies on hatched larvae of Culex pipiens

The attract‐and‐kill strategy is a new pest management technique that presupposes the intelligent combination of an attracting agent (e.g. pheromone) and a killing agent (e.g. insecticide). In the present study, the potential combination of the microencapsulated synthetic oviposition pheromone 6‐acetoxy‐5‐hexadecanolide with an insecticide has been tested. Initially, polyurea microcapsules containing 6‐acetoxy‐5‐hexadecanolide, the synthetic mixture of diastereomers of the oviposition pheromone of the mosquito species Culex quinquefasciatus Say (Diptera: Culicidae), were studied. Laboratory bioassays were performed to confirm the bioactivity of the microencapsulated pheromone on the oviposition activity of Culex pipiens L. biotype molestus Førskal (Diptera: Culicidae) with the aim of determining the optimum dose for oviposition response. Its effect was dose dependent, revealing an optimum dose of 300 mg of dried microcapsules. Attractancy over time was also studied. The microencapsulated pheromone was found to be sufficiently attractive to gravid female mosquitoes for a period of 40 days. Finally, the combination of the synthetic pheromone with the control agent temephos showed both an acceptable oviposition activity and sufficient larvicidal effect. Copyright © 2007 Society of Chemical Industry     

含氟昆虫性信息素的研究进展及应用前景

以氟原子取代性信息素上的氢原子,能够影响天然性信息素的化学、生物学和物理性质。氟原子的取代位点一般分为烷基链取代、双键取代和极性基团取代3类。含氟昆虫性信息素或类似物具有增效、激活、拮抗、抑制等多种生物活性,在害虫的预报和综合防治上具有着良好的应用前景。本文就国内外学者对昆虫性信息素含氟取代物的研究进展展开综述,并预测了其应用前景。     

Dialkyl phosphorofluoridates and alkyl methylphosphonofluoridates as disruptants of moth sex pheromone-mediated behavior

A series of dialkyl phosphorofluoridates and alkyl methylphosphono-fluoridates in which one or two of the alkyl moieties were long-chain alkyl groups were synthesized and examined for their ability to disrupt moth sex pheromone-mediated behavior of the oriental fruit moth, Grapholita molesta. Disruption of pheromone-mediated behavior was found only for those compounds containing a (Z)-8-dodecenyl moiety, i.e. the alkyl substituent of the principal pheromone component ((Z)-8-dodecenyl acetate) of the oriental fruit moth. Di-((Z)-8-dodecenyl) phosphorofluoridate was nearly as disruptive as (Z)-8-dodecenyl acetate.     

粉螨性信息素(R)-2,6-二甲基-5-庚烯-1-醇的不对称合成

粉螨Tyreophagus sp. 包括许多危害农作物的重要害虫和仓储害虫,而(R)-2,6-二甲基-5-庚烯-1-醇为粉螨 性信息素的主要成分。本研究首次利用Evans手性助剂法构建该性信息素的手性叔碳中心,以戊醛酸甲酯为原料,经过Wittig偶联、LiOH水解、甲基化及硼氢化钠还原等6步反应,完成了该信息素的不对称合成。     

Some fluorine-containing pheromone analogues

Two analogues of the aphid alarm pheromone (E)-β-farnesene, a trifluorofarnesene and a difluoro-1-norfarnesene, were found to be highly active and were more readily detectable than the parent compound. For (Z)-hexadec-11-enal, a component of some lepidopteran sex attractant pheromones, replacement of the carbonyl oxygen with a difluoromethyl group to give a difluoroheptadecadiene resulted in loss of activity. A trifluoroacetoxyhexadecanolide was a more volatile analogue of the mosquito oviposition pheromone (?)-(5R,6S)-6-acetoxy-5-hexadecanolide and was highly active.     

Synthesis of allylic trifluoromethyl ketones and their activity as inhibitors of the sex pheromone of the leopard moth, Zeuzera pyrina L. (Lepidoptera: Cossidae)

BACKGROUND: Trifluoromethyl ketones (TFMKs), structurally related to the pheromones, are good inhibitors of pheromone communication in insects. To determine their activity on Zeuzera pyrina L. (Lepidoptera: Cossidae), a polyphagous pest, the authors have prepared two diunsaturated TFMK analogues of the major (3) and the minor (4) pheromone components, and two monounsaturated ones (5, 6). Their biological activity in electroantennogram (EAG), wind tunnel and field tests is presented. RESULTS: The synthetic strategy to obtain the allylic TFMKs 3 and 5 is based on the reactions of diene 10 and 1‐octadecene with trifluoroacetaldehyde ethyl hemiacetal, followed by Dess–Martin oxidation of the resulting homoallylic trifluoromethyl alcohols. In EAG, topical application of analogues 3 and 4 on male antennae significantly reduced the pheromone response. In the wind tunnel, compound 4 reduced the number of contacts with the pheromone source. In the field, traps baited with mixtures of pheromone and inhibitors captured significantly fewer males than the pheromone alone. CONCLUSION: An efficient synthesis of allylic TFMKs is reported, with good overall yield, regiospecificity and diastereoselectivity. These compounds are good inhibitors of the pheromone in electrophysiology, wind tunnel and field tests. The results show the importance of two unsaturations at positions 2 and 13 of the trifluoroacyl group in the structure of the analogues, the latter being critical for inhibitory activity. Copyright © 2011 Society of Chemical Industry     

Synthesis and Herbicidal Activity of Substituted Tetrahydronaphthalenes (Part II)

This paper reports the synthesis and the biological activity of novel tetrahydronaphthalenes with substitution of functional groups at each position of the aromatic ring and substitution of various alkyl groups at the 1-position of the non-aromatic ring. These compounds exhibited pre-emergent herbicidal activity which was determined by the orientation and type of functional groups on the aromatic ring with the 1,1-dimethyl substitution on the non-aromatic ring. The activity tended to be highest for nitro or methyl at the 5- and 7-positions with an amino or ester group at the 6-position and a dimethyl substitution at the 1-position.     

甜菜夜蛾性信息素组分的鉴定及其田间试验

采用气相色谱仪(GC)及气质联用仪(GC-MS)等技术对我国甜菜夜蛾性信息素组分的鉴定结果表明,雌蛾性信息素腺体中含有4种组分,分别为Z9,E12-14:Ac(A)、Z9-14:OH(B)、Z9-14:Ac(C)和Z9,E12-14:OH(D);田间和室内种群各组分的比例(A:B:C:D)分别为47:18:18:17和43:18:23:16,比例及滴度在两种群间未有显著差异;雄蛾田间引诱测定表明,组分A、B显示性信息素活性。几种不同配比的硅橡胶塞诱芯在田间均显示极高的诱蛾活性,以9:1的AB二元诱芯(剂量100μg)最高,其诱蛾量与黑光灯相当,两者呈显著的正相关性,表明该诱芯可替代黑光灯用于甜菜夜蛾的种群测报。利用性诱捕器进行田间种群监测显示,1999年浙江省慈溪市的甜菜夜蛾共发生6代,以第4、5代发生量最高。     

Field electroantennogram and trap assessments of aerosol pheromone dispensers for disrupting mating in Epiphyas postvittana

An electronically controlled aerosol system for mating disruption was evaluated against Epiphyas postvittana Walker in apple orchards in New Zealand. The area in which male moths were affected by the aerosol system was examined using catches in traps radiating from a central single-point source of either one aerosol can dispenser or 100 polyethylene tubing dispensers, compared with catches in orchard plots without pheromone dispensers. Both pheromone dispensing systems decreased moth catch to similar levels at 5-10 m from the central release point, but there was 5.5-fold more pheromone released from aerosol cans than from polyethylene dispensers over a 24 h period. Trap catches were reduced by about 90% in plots treated with either five aerosol cans per hectare or uniform deployment of polyethylene dispensers. Recordings of electroantennograms in open grassed plots and orchards indicated that the treated cotton pad of an aerosol dispenser and a point source of 100 polyethylene tubing dispensers produced similar electroantennogram recordings. Electroantennogram recordings provided evidence that pheromone plume detection from a single-point source was maintained over a range of 5-40 m downwind in the orchard. On present evidence, aerosol pheromone dispensers could not be recommended for further testing towards control of E. postvittana under New Zealand conditions owing to their higher cost of purchase and operation.     

Field evaluation of the synthetic female sex pheromone of the citrus flower moth,Prays Citri (mill.) (Lepidoptera: Yponomeutidae), and related compounds

The synthetic female sex pheromone ofPrays citri, (Z)-7-tetradecenal, proved to be highly attractive to male moths in the field when released from a variety of dispensers in five different designs of sticky trap. When the pheromone was released from impregnated polyethylene vials, a wide range of initial loadings from 10 μg to 20 mg was attractive, and loadings of 40 μg and above were more attractive than a virgin female moth. Initial loadings of 0.5 mg and 1.0 mg remained attractive for at least five months in the field. Release rates of pheromone from the polyethylene vials under constant laboratory conditions were measured for two different initial loadings. Other isomers of the pheromone and a pheromone ‘mimic’, (Z)-5-dodecenyl formate, were unattractive to male moths and did not affect the attractiveness of the synthetic pheromone or of a virgin female moth.     

Inhibition of pheromone action in Sesamia nonagrioides by Haloacetate analogues

The electrophysiological activity of some halogenated analogues of the major component of the sex pheromone of the corn stalk borer Sesamia nonagrioides Lef. (1) is presented. The analogues comprise a series of fluoro-, chloro- and bromoacetate analogues 4 – 10 as well as trifluoromethyl ketone 11. The fluoro derivatives 4 – 6 displayed remarkable electro-antennogram (EAG) intrinsic activities in comparison with the parent acetate 1, while the remaining analogues elicited significantly lower response. The compounds have also been tested as inhibitors of the sex pheromone perception in EAG and in the field. In the laboratory. fluoro analogues 4 – 6 were better inhibitors than chloro derivatives 7 – 9 , which in turn behaved similarly to the bromoacetate 10 . Trifluoromethyl ketone 11, however, was a poor inhibitor of the pheromone action. In the field, baits of mixtures of compounds 5 – 11 with the corn stalk borer pheromone in 10 :1 ratio inhibited the concomitant attraction of the clover cutworm moth Scotogramma irifolii Rott., while the difluoro analogue 5, trichloroacetate 9 and trifluoromethyl ketone 11 also diminished the number of catches of the armyworm Mythimna unipuncta Haw. The monofluoroacetate 4. trifluoro analogue 6 and bromo derivative 10 significantly disrupted the pheromone action of the corn borer, whereas trifluoromethyl ketone 11 synergistically increased the number of males attracted to the pheromone trap alone. Addition of 11 to baits containing the corn borer pheromone caught S. nonagrioides selectively with regard to the other habitat-sharing species M. unipuncta and S. trifolii.     

青岛地区暗黑鳃金龟性信息素鉴定及田间应用技术

为深入了解国内暗黑鳃金龟Holotrichia parallela Motschulsky种群的性信息素组分及其田间引诱效果,采用气质联用技术对其雌性信息素进行了分离鉴定,利用标记-回捕技术测试了5 h内暗黑鳃金龟的扩散距离,并在此基础上测试了诱捕器颜色、离地高度、密度、单诱芯性信息素含量等对田间诱虫效果的影响。结果表明：L-异亮氨酸甲酯和（R）-（-）-芳樟醇为国内青岛种群暗黑鳃金龟雌虫性信息素的主要组分,两者含量比为7：1;暗黑鳃金龟5 h扩散距离可达400 m以上,平均扩散距离为55.9 m,扩散距离在20~60 m的个体占总虫数的77.5%;黄色诱捕器对该虫的引诱效果显著优于黑色和绿色;诱捕器离地2 m引诱到的试虫数目显著高于1、1.5、2.5和3 m;单个诱芯性信息素含量360 mg引诱效果最好,显著高于180 mg及以下浓度;诱捕器间隔20~60 m防治效果较好,结合使用成本和试虫扩散距离,间距60 m最优。     

Sex Pheromone Traps for Monitoring the European Vine Moth,Lobesia botrana: Effect of Dispenser Type,Pheromone Dose,Field Aging of Dispenser,and Type of Trap on Male Captures

The effects of dispenser type, pheromone dose in the dispenser, aging of dispenser in the field, and trap type on trapping efficiency of males of the European vine moth,Lobesia botrana Den. et Schiff. (Lepidoptera: Tortricidae), were investigated. LB Pherocon caps and locally manufactured septa were equally effective in attracting males to traps. Within the range of 0.1 to 100 μg pheromone/dispenser, response of males increased positively with the pheromone dose. Within the first 7 days tested, pheromone loads of 1 or 10 mg/dispenser were significantly less attractive to males than 0.1 mg/dispenser. The effect of aging of the dispenser (loaded with 1 mg pheromone) in the field on trapping efficiency was significant. Captures in traps baited with 4- and 5-week-old septa were significantly lower (by 24%) than those in traps baited with 1-week-old septa. The fairly slow loss of attractancy exhibited by rubber septa indicates that septa may be kept in traps for at least 5 weeks. The release rate of the pheromone from the Israeli dispensers (1 mg loaded) was measured in a flow system. The emission of the pheromone decreased gradually as a function of age, correlating well with the lower trap catches of field-aged septa. Release rates were reduced by 56%, 70% and 84% after 4, 5 and 6 weeks, repectively. The nonsticky IPS trap was as effective in capturing the European vine moth males as the sticky Pherocon 1C trap. The possibility of using the non-sticky, nonsaturating and easy-to-handle IPS traps may lead to better and easier monitoring of the European vine moth populations.     

两种罗索线虫对不同蚊种的自然感染及实验研究

1984年在河南信阳地区发现两种蚊体寄生索线虫,在同一孳生地内生长繁殖,分别寄生于中华按蚊和致倦库蚊及三带喙库蚊等幼虫体内,自然寄生率为5.48％、4.32％、5.82％。通过人工感染试验,感染率均较高,可达61.5％～95.7％。试验证明两者对按蚊和库蚊具有显然不同的生理特性。这两种罗索线虫在稻田、田沟等多种水体内均有孳生,宿主范围广泛,有应用价值。     

亚致死剂量溴氰菊酯对亚洲玉米螟雄蛾性信息素通讯行为的影响

用亚致死剂量溴氰菊酯处理亚洲玉米螟雄蛾后,存活雄蛾对信息素定向行为反应受到较大的影响。雄蛾的起飞潜伏期延长,不应率增加,到达诱芯率大幅度下降。反应下降程度与剂量的相关性显著。以雄蛾的行为反应率机率值(Z)对药剂处理剂量对数(X)和处理天数(Y)进行二元回归分析,回归方程分别为:起飞:Z=6.979-6.559X 0.162Y;定向:Z=5.258-2.611X-0.039Y;逆飞:Z=4.982-2.457X-0.061Y;到达:Z=3.399-1.011X 0.168Y。     

Night observations on the cotton leafworm,Spodoptera littoralis: Reliability of pheromone traps for population assessment and efficacy of widely separated pheromone dispensers for mating disruption

Night observations on the cotton leafworm,Spodoptera littoralis (Boisd.) (Lepidoptera: Noctuidae), were conducted in pheromone-treated and untreated plots in which males, females, mating pairs on plants, and males caught in traps were collected. Results indicated that emergence of a new population was rapid (8-9 days) and that the number of virgin females and of mating pairs on plants reached a peak 5–6 days prior to that of males captured in pheromone traps. Males responded to pheromone traps most actively when the actual virgin female popution had already declined considerably. Dispensers adsorbed with(Z,E)-9,11-tetradecadienyl acetate and located 25 m apart, effectively reduced male captures in traps. However, the number of native mating pairs observed in the treated field during the night was not reduced. Few releasers at wide spacing, even with high amounts of the major pheromonal component, were ineffective in causing mating disruption ofSpodoptera littoralis.     

Studies on herbicidal carbamoyltetrazolinone derivatives: Selection of fentrazamide

1-Phenyl-5(4 H )-4-dialkylcarbamoyltetrazolinones represent a new class of herbicides that are active against barnyardgrass ( Echinochloa spp.) in paddy fields. To select the most favorable compound as a paddy herbicide, herbicidal activity and selectivity of the carbamoyltetrazolinone compounds to transplanted rice were determined in greenhouse tests. Higher herbicidal activities were associated with the compounds having a 2-Cl- or 2-Cl-6-Me-substituted or an unsubstituted phenyl ring, and a combination of C_2–3 linear alkyl group and a C₄ branched-chain alkyl or a C_5–6 cycloalkyl group on the nitrogen atom in the carbamoyl structure. In addition, the compounds carrying a total of seven to nine carbon atoms in the substituents on the carbamoyl nitrogen exhibited a good selectivity between barnyardgrass and transplanted rice plants. From the results of soil thick-layer chromatography, the good crop compatibility of carbamoyltetrazolinones was correlated to the mobility of the compounds in paddy soil. The investigation resulted in the selection of an excellent compound, 4-(2-chlorophenyl)- N -cyclohexyl- N -ethyl-4,5-dihydro-5-oxo-1 H -tetrazole-1-carboxamide (common name: fentrazamide), as a rice paddy herbicide for controlling barnyardgrass.     

Pheromone Research and Development in Israel 1975–2015

The review describes the history of pheromone research in Israel in 1975–2015. The research focused on sex pheromones of moths that were important agricultural pests. Identification, synthesis and field application of sex pheromones was performed. Synthetic procedures of several known sex pheromones were developed. Monitoring and control of key pest moths was evaluated. The interactions of pheromone components of closely related species were studied in field and laboratory experiments. The sex pheromones of three scale insects, two mealybug species and Matsucoccus josephi were studied. New syntheses were developed and the pheromones were implemented in pest management. Structure activity relationship of the pheromonal and kairomonal of the M. josephi pheromone was investigated. Different pherotypes of P. ficus were identified and evaluated. The aggregation pheromone of sap beetles in combination with food baits was evaluated. The aggregation pheromone of the almond bark beetle was identified and a stereospecific synthesis of its enantiomers was developed. Monitoring the pest in stone fruit orchards was implemented. The activity of the pheromone biosynthesis activating neuropeptide (PBAN) was studied in Helicoverpa armigera and Heliothis peltigera. The ligation technique was used to assess the effect of PBAN on the production of female and male pheromones. A structure-activity relationship study of PBAN indicated that shorter peptides display activity as the full length PBAN. A series of linear and cyclic peptide analogs was prepared, resulting in the discovery of a lead antagonist. The research and development activity facilitated the intensive integration of pheromones in the pest management regimes in Israeli agriculture.     

Development of a pheromone trap monitoring system for orange wheat blossom midge, Sitodiplosis mosellana, in the UK

Field-trapping experiments with synthetic 2,7-nonadiyl dibutyrate, the female-produced sex pheromone of the orange wheat blossom midge, Sitodiplosis mosellana (Géhin), demonstrated that pheromone traps were highly attractive to males and caught very few non-target organisms. Different formulations of pheromone were tested to identify the optimum release rate and dispenser type for use in pheromone traps in the UK. Key findings were that racemic pheromone was as effective as enantiomerically pure (2S,7R)-2,7-nonadiyl dibutyrate, that release rates higher than 0.5 microg day(-1) were not necessary and that the optimal formulation was a 1 mg pheromone loading in a rubber septum. Pheromone traps gave a reliable indication of peak midge emergence, onset of flight and abundance of midges throughout the season. A strong correlation between maximum trap catch and crop infestation levels was obtained.     

Preparation and biocidal activity of alkyl phenyl (dichloromethyl)phosphonates

Seventeen new alkyl (or phenacyl) phenyl (dichloromethyl)phosphonates were synthesised; seven of these showed poor fungicidal activity when tested in vitro against Pyricularia oryzae but some possessed high insecticidal activity against Culex fatigans and Drosophila melanogaster.