Identification of unique pheromone components for soybean looper mothPseudoplusia includens

Analysis of sex pheromone glands from individual female soybean looper moths showed that in addition to the previously identified main component (Z)-7-dodecenyl acetate, the compounds dodecyl acetate, 11-dodecenyl acetate, (Z)-7-dodecenyl propionate, and (Z)-7-dodecenyl butanoate were also produced. Two of the components, 12OAc and 11–12OAc, were not detected in a single analysis of female effluvium. Flight-tunnel tests showed that the five-component and three-component blends were equal to each other and to a female extract (> 80% source contacts) and that the mixtures were superior toZ7–12OAc alone. Field tests indicated that the five-component blend was significantly more attractive thanZ7–12OAc alone at a dosage of 1 mg, but that the blend was only slightly better at 3 mg.     

Identification of a four-component sex pheromone of the female oriental fruit moth,Grapholitha molesta (Lepidoptera: Tortricidae)

The female-emitted pheromone ofGrapholitha molesta (Busck), the Oriental fruit moth, was collected by holding females in glass flasks during calling. Flask washes were found to contain four pheromone components: (Z)-8-dodecenyl acetate and (E)-8-dodecenyl acetate in a 1007 ratio, and (Z)-8-dodecen-1-ol and dodecanol in a 10020 ratio. The ratio of (Z)-8-acetate to (Z)-8-dodecen-1-ol was approx. 10030. Approximately 0.1–0.2 ng of pheromone was recovered per female per hour of calling.Published as Journal Article No. 8598 of the Michigan State University Agricultural Experiment Station.     

Sex pheromone ofAdoxophyes orana: Additional components and variability in ratio of (Z)-9- and (Z)-11-tetradecenyl acetate

Twelve products related to the sex pheromone main components (Z)-9- and (Z)-11-tetradecenyl acetate (Z9–14Ac andZ11–14Ac, respectively), were identified in female pheromone gland extracts of the laboratory-reared summerfruit tortrix moth,Adoxophyes orana F.v R. These are the geometric isomers and the alcohols of the main components, (Z)-9-dodecenyl acetate, (Z)-11-hexadecenyl acetate, and saturated acetates of 12–22 carbons. The ratio ofZ9–14Ac toZ11–14Ac in individuals varied from 3.51 to 111 with an average of 6.2; their total added up to 462 ng/female with an average of 182 ng for 2- to 7-day-old individuals. No qualitative or quantitative differences were observed between laboratory and field insects.Z9–14Ac,Z11–14Ac and the corresponding alcohols were also found in female effluvia. Addition of either of the two alcohols to a blend of the two acetates augmented trap catch in the field. The same was true for (Z)-9,(E)-12-tetradecadienyl acetate which was not detected in gland extracts.     

Isolation, Identification, Synthesis, and Field Evaluation of the Sex Pheromone of the Brazilian Population of Spodoptera frugiperda

Several studies have shown intraspecific geographical variation in the composition of sex pheromones. Pheromone lures from North America and Europe were not effective against the fall armyworm Spodoptera frugiperda (Smith, 1797) (Lepidoptera: Noctuidae) in Brazil, so we examined the composition of the sex pheromone produced by females from Brazilian populations. Virgin female gland extracts contained (Z)-7-dodecenyl acetate (Z7-12:Ac), (E)-7-dodecenyl acetate (E7-12:Ac), dodecyl acetate, (Z)-9-dodecenyl acetate, (Z)-9-tetradecenyl acetate (Z9-14:Ac), (Z)-10-tetradecenyl acetate, tetradecyl acetate/(Z)-11-tetradecenyl acetate (Z11-16:Ac), and (Z)-11-hexadecenyl acetate. The relative proportions of each acetate were 0.8:1.2:0.6:traces:82.8:0.3:1.5:12.9, respectively. This is the first time that E7-12:Ac has been reported from the pheromone gland of S. frugiperda. Only three compounds, Z9-14:Ac, Z7-12:Ac, and E7-12:Ac, elicited antennal responses, and there were no differences in catch between traps baited with either Z7-12:Ac + Z9-14:Ac or Z7-12:Ac + Z9-14:Ac + Z11-16:Ac blends. However, the Z7-12:Ac + Z9-14:Ac + E7-12:Ac blend was significantly better than Z7-12:Ac + Z9-14:Ac, indicating that E7-12:Ac is an active component in the sex pheromone of the Brazilian populations of S. frugiperda.     

Sex pheromone of the chokecherry leafroller moth,Sparganothis directana

(E)-9,11-Dodecadienyl acetate and (Z)-9,11-dodecadienyl acetate in conjunction with (E)-11-tetradecenyl acetate and (Z)-11-tetradecenyl acetate were found to comprise the sex pheromone ofSparganothis directana, based on chemical analysis, electroantennogram tests, and field trapping. (E)-9-Dodecenyl acetate and (Z)-9-dodecenyl acetate were also found in gland extracts but did not influence trap catches. The relative amounts of these compounds in the gland were 3521928 106, in the order named. Only (E)-9,1 1-dodecadienyl acetate, (E)-11-tetradecenyl acetate, and (Z)-11-tetradecenyl acetate were required for attraction of males to traps, dispensed in the relative amounts 501238, respectively.Lepidoptera: Tortricidae.Supported by National Science Foundation grant PCM 78-13241.     

Identification of sex pheromone components of redbacked cutworm,Euxoa ochrogaster,and modification of sex attractant blend for adult males

Pheromone washes from calling female moths of redbacked cutworm,Euxoa ochrogaster (Guenée), contained the following acetates that are structurally similar to those of known lepidopteran pheromones (%): decanyl (8.7), dodecanyl (8.5), (E)-5-dodecenyl (3.3), (Z)-5-dodecenyl (76.4), (Z)-7-dodecenyl (3.1), and (Z)-9-dodecenyl (trace<0.5%). This is the first time that (Z)-5-dodecenyl acetate has been identified as a pheromone component. Three types of specific receptor cells were found in the male antennae, and they responded to (Z)-5-decenyl acetate, (Z)-5- and (Z)-7-dodecenyl acetates, respectively. Strong electroantennographic detector responses were also recorded for these three acetates and for (Z)-5-undecenyl acetate. The evidence for the presence of (Z)-5-decenyl acetate in the pheromone washes was inconclusive. The presence of (Z)-7- and the absence of (Z)-8-dodecenyl acetates were confirmed by a special electroantennographic detector technique in which the detector antennae were from males of other species that were known to have strong responses to these acetates. This is a very useful technique. Field results show that low concentrations (0.1–1.3%) of (Z)-5-decenyl acetate were synergistic when tested in a previously reported blend, but 6% was inhibitory. Similarly, (Z)-7-dodecenyl acetate at 2% or less may be essential for the attraction of males, but in previous tests at 14% it also was inhibitory. Species-specific attractant blends for redbacked cutworm males are described.Lepidoptera: Noctuidae     

Sex pheromone of purplestriped shootworm,Zeiraphera unfortunana powell

The analyses of virgin female sex pheromone gland extracts and gland volatiles by GC, GC-EAD and GC-MS, followed by field trapping experiments, have identified (E)-9-dodecenyl acetate (E9–12Ac) as the primary sex pheromone component of the purplestriped shootworm,Zeiraphera unfortunana. Dosages of 1.0–10.0 g ofE9–12Ac impregnated in rubber septa provide an effective trap bait and can be used for monitoring purposes.Lepidoptera: Tortricidae.     

Sex Pheromone of Apple Blotch Leafminer, Phyllonorycter crataegella, and Its Effect on P. mespilella Pheromone Communication

(Z)-10,(Z)-12-Tetradecadienyl acetate (Z10,Z12–14:OAc) and (E)-10,(E)-12-tetradecadienyl acetate (E10,E12–14:OAc) are sex pheromone components of the apple blotch leafminer (ABLM), Phyllonorycter crataegella. Compounds extracted from female pheromone glands were identified by coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses, retention index calculations of EAD-active compounds, and by comparative GC-EAD analyses of female ABLM-produced and authentic (synthetic) compounds. In field experiments in apple Malus domestica orchards in Connecticut, Z10,Z12–14:OAc alone attracted ABLM males. Addition of E10,E12–14:OAc to Z10,Z12–14:OAc at 0.1:10 or 1:10 ratios enhanced attractiveness of the lure. Geometrical isomers Z10,E12- or E10,Z12–14:OAc at equivalent ratios were behaviorally benign and slightly inhibitory, respectively. In field experiments in British Columbia, Z10,Z12–14:OAc plus E10,E12–14:OAc did not attract Phyllonorycter moths, supporting the contention that ABLM is not present in the fruit growing regions of British Columbia. Z10,Z12–14:OAc added to P. mespilella pheromone, (E)-4,(E)-10-dodecadienyl acetate, strongly inhibited response by P. mespilella males. Recognition of the ABLM pheromone blend by allopatric P. mespilella males suggests a phylogenetic relationship and previous sympatry of these two Phyllonorycter spp. If pheromonal attraction of ABLM males were reciprocally inhibited by P. mespilella pheromone, a generic Phyllonorycter pheromone blend could be tested for pheromone-based mating disruption of the apple leaf-mining Phyllonorycter guild in North America.     

Identification of female sex pheromone components of rice looper,Plusia festucae (L.), (Lepidoptera: Noctuidae)

The rice looper,Plusia festucae, is a defoliator of the rice plant. Chromatographic behavior, chemical reactions, and GC-MS analyses of the female sex pheromone revealed that the main component was (Z)-5-dodecenyl acetate (Z5–12: OAc, component I). The GC-MS analysis also indicated that the pheromone gland extract included another three monounsaturated components, (Z)-5-dodecen-l-ol (Z5–12: OH, component II), (Z)-7-tetradecenyl acetate (Z7–14: OAc, component III), and (Z)-7-tetradecen-l-ol (Z7–14: OH, component IV) in the following ratio: I:II:III:IV=100:6:15:1. In a paddy field, the mixture of synthetic I, II, and III in a ratio of 100:6:15 showed stronger attractancy than the virgin female, while the role of IV was unknown.     

Sex pheromone of cranberry fruitworm,Acrobasis vaccinii riley (Lepidoptera: Pyralidae)

The following compounds and (approximate ratios) were identified in sex pheromone gland extracts of femaleAcrobasis vaccinii Riley by comparison of gas chromatography-mass spectrometric traces with those of synthetic standards: (E,Z)-, (Z,E)-, (Z,Z), and (E,E)-8, 10-pentadecadien-l-ol acetates (100:1:2:12), a dodecen-l-ol acetate (8), (Z)-8-, (Z)-9-, and (E)-9-pentadecen-l-ol acetates (3:23:4), two heptadecen-l-ol acetates (4:4), tetradecyl, pentadecyl, hexadecyl, and heptadecyl acetates (3:15:10:8), dodecan-l-ol (6), tetradecan-l-ol (5), and hexadecan-l-ol (23). The amount of (E,Z)-8, 10-pentadecadien-l-ol acetate (E8,Z10–15:Ac) in the extract was about 0.5 ng/female. Electroantennographic analysis of gas chromatographic fractions of female sex pheromone gland extract showed that the fraction containingE8,Z10–15:Ac elicited the greatest response. Alone,E8,Z10–15:Ac failed to elicit upwind flight of males in flight-tunnel tests, and traps baited with it did not catch males in field experiments. WhenE8,Z10–15:Ac was combined with (E)-9-pentadecen-l-ol acetate (100:4), male upwind flight response in flight-tunnel tests was equivalent to those obtained with extract of female sex pheromone glands (synthetic, 62%; natural, 51%), but the percent of males flying upwind that contacted the source was lower (synthetic, 47%; natural, 88%). The lower percent of source contact elicited by the synthetic pheromone could be a result of the difference in isomer ratios of 8,10–15:Ac in the natural and synthetic pheromone or could indicate that the synthetic pheromone is incomplete. Traps baited with the 100:4 combination caught large numbers of males in field experiments.     

Identification and Field Evaluation of Components of Female Sex Pheromone of Millet Stem Borer, Coniesta ignefusalis

Five active compounds were detected during analyses of ovipositor washings and effluvia from virgin female Coniesta ignefusalis moths by gas chromatography (GC) linked to electroantennographic (EAG) recording from a male moth. These were identified as (Z)-7-dodecen-1-ol (Z7–12:OH), (Z)-5-decen-1-ol (Z5–10:OH), (Z)-7-dodecenal (Z7–12:Ald), (Z)-7-dodecenyl acetate (Z7–12:Ac), and (Z)-9-tetradecen-1-ol (Z9–14:OH) by comparison of their GC retention times, mass spectra, and EAG activities with those of synthetic standards. Laboratory tests of dispensers for these compounds showed that release rates from polyethylene vials increased to relatively uniform values after three to four days, but release from septa was very rapid and nonuniform and decreased to low levels after two to three days. Trapping tests in Niger showed that the major component, Z7–12:OH, and two of the minor components, Z5–10:OH and Z7–12:Ald, were essential for attraction of male C. ignefusalis moths. The most attractive blend contained these three components in a 100:5:3.3 ratio in a polyethylene vial, which emitted the components in similar proportions to those produced by the female C. ignefusalis moth. Water traps baited with this blend containing 1 mg of Z7–12:OH caught more male C. ignefusalis moths than traps baited with newly emerged female moths. Addition of up to 10% of the corresponding E isomers of the pheromone components had no effect on catches, but addition of the other two minor components detected, Z7–12:Ac and/or Z9–14:OH, to the attractive blend at naturally occurring levels caused significant reductions in trap catch.     

Sex pheromone of tomato fruit borer, Neoleucinodes elegantalis

Five candidate pheromone components were identified by analyzing pheromone gland extracts by gas chromatography (GC), coupled GC-electroantennographic detection (EAD), and coupled GC-mass spectrometry (MS): (E)-11-hexadecenol(E11–16 : OH), (Z)-11-hexadecenol (Z11–16 : OH),(E)-11-hexadecenal, (E)-11-hexadecenyl acetate, and (Z)-3,(Z)-6,(Z)-9-tricosatriene (Z3,Z6,Z9–23 : Hy). In electroantennogram (EAG) recordings, synthetic E11–16 : OH elicited stronger antennal responses at low doses than other candidate pheromone components. Field tests demonstrated that synthetic E11–16 : OH as a trap bait was effective in attracting males, whereas addition of Z11–16 : OH inhibited the males' response. Z3,Z6,Z9–23 : Hy strongly enhanced attractiveness of E11–16 : OH, but was not attractive by itself. A pheromone blend with synergistic behavioral activity of an alcohol (E11–16 : OH) and hydrocarbon (Z3,Z6,Z9–23 : Hy) component is most unusual in the Lepidoptera. The synthetic two-component pheromone is approximately 60 times more attractive than the female-produced blend and might facilitate the control of this pest.     

Sex pheromone ofEupoecilia ambiguella female: Analysis and male response to ternary blend

Sex gland extracts and washes ofEupoecilia ambiguella contain 10–20 ng/female of the primary sex pheromone componentZ-9-dodecenyl acetate (Z9–12Ac), accompanied by a number of related compounds. These areE-9-dodecenyl acetate (E9–12Ac),Z-9-dodecen-1-ol (Z9–12OH), saturated acetates of 12, 16, 18, and 20 carbons, and traces of a doubly unsaturated acetate, tentatively identified as a 9,11-dodecadienyl acetate. Octadecyl acetate predominates among the pheromone-related components, making up 1–2, occasionally 20–30 times the amount ofZ9–12Ac. The same compounds were also found in field-collected females and in effluvia.Z-9-Undecenyl acetate, which is a male attractant on its own, was also found in a sample of female effluvia. A hierarchy is observed in the ethological function of the pheromone components.Z9–12Ac is an attractant forE. ambiguella males. Dodecyl acetate (12Ac) is not attractive on its own but augments male catch when added to the main attractant. Addition of 18Ac augments attraction only when bothZ9–12Ac and 12Ac are present. Windtunnel tests demonstrate that 18Ac also raises the disorientation threshold, as previously shown for 12Ac. Other compounds, with the possible exception of additional saturated acetates, had either no effect on trap catch or, in the case ofE9–12Ac,Z9–12OH, andE-9,11-dodecadienyl acetate, were inhibitory above a certain level. A blend of roughly equal parts ofZ9–12Ac, 12Ac, and 18Ac provides the best attractant blend forE. ambiguella known to date.     

Sex Pheromone of the Cranberry Blossom Worm, Epiglaea apiata

The cranberry blossom worm, Epiglaea apiata (Grote) (Lepidoptera: Noctuidae), is a major pest of cranberries in New Jersey. The female sexpheromone of this moth was identified as a blend of (Z)-9-hexadecenyl acetate (Z9-16:Ac), (Z)-9-tetradecenyl acetate (Z9-14:Ac), and tetradecyl acetate (14:Ac) by gas chromatographic–electroantennographic detection and gas chromatography–mass spectrometry. The ratio of the components in extracts of the female pheromone gland was determined to be 65 : 2 : 33 of the Z9-16:Ac, Z9-14:Ac, and 14:Ac, respectively. The double bond positions of the pheromone components were confirmed by dimethyl disulfide derivatization. In addition to the above three components, a mixture of C₄–C₁₀ aliphatic acids was present in both gland extracts and effluvia collections, and the acids elicited significant EAD responses from male moth antennae. However, addition of the C₄–C₁₀ aliphatic acids to the pheromone blend did not significantly increase trap captures. Three-hundred- and 1000-g doses of a synthetic blend containing Z9-16:Ac, Z9-14:Ac, and 14:Ac (65 : 2 : 33), on a rubber septum were more attractive to males than lower doses.     

Individual variation in the pheromone of the turnip moth,Agrotis segetum

Female turnip moths (Agrotis segetum) from a laboratory culture inbred for more than 30 generations, and the offspring (first and third generation) from field-collected insects were analyzed individually for acetates and alcohols in the pheromone gland. Quantitative analysis of individual components was performed at the subnanogram level by gas chromatographymass spectrometry (selected ion monitoring). The titer of the pheromone, i.e., the sum of the homologous acetates (Z)-5-decenyl acetate, (Z)-7-dodecenyl acetate, and (Z)-9-tetradecenyl acetate was 2.0 ± 0.3 ng in the laboratory culture and 3.2 ± 0.6 ng in the wild strain. There was no correlation between pheromone titer and female weight. The relative proportion of the pheromone components varied substantially between individuals, but there was no statistically significant difference between the two populations. The percentages of the respective compounds (¯X ± coefficient of variation) were 14.8 ± 127% for Z5-10:OAc, 55.6 ± 32% for Z7-12:OAc, and 29.6 ± 59% forZ9-14:OAc. The pheromone composition varied more in the wild strain than in the laboratory culture. The significance of the pheromone variation to the attraction of males was tested in a field experiment. The ratio of males trapped by the most attractive blend versus the least attractive one was 2.2.Schiff., Lepidoptera: Noctuidae.This study was made within the Swedish project Odour Signals for Control of Pest Insects.     

Sex Attractant Pheromone of Saturniid Moth Coloradia velda

The female-produced sex attractant pheromone of Coloradia velda has been identified by a combination of analytical methods and field tests as a blend of (10E,12Z)-hexadecadien-1-yl acetate (10E,12Z–16:Ac), (10E,12E)-hexadecadien-1-yl acetate (10E,12E–16:Ac), and (10E,12Z)-hexadecadien-1-ol (10E,12Z–16:OH) in a 10:1:0.33 ratio, respectively. The corresponding aldehyde (10E,12Z–16:Ald) was also found in extracts of female pheromone glands, but in blends with 10E,12Z–16:Ac and 10E,12E–16:Ac at low doses did not significantly increase the attractiveness of baits to male moths.     

Behavioral responses of male turnip moths,Agrotis segetum,to sex pheromone in a flight tunnel and in the field

The response of individual male turnip mothsAgrotis segetum was observed in a sustained flight tunnel to a mixture of decyl acetate, (Z)-5-decenyl acetate, (Z)-7-dodecenyl acetate, and (Z)-9-tetradecenyl acetate in proportions similar to those found in gland extracts from virgin females (0.6: 1:5:2.5). Lures containing 3–30 g (Z)-5-decenyl acetate proved to be maximally attractive, with approximately 60% of the males completing all behavioral steps from activation to copulation efforts. A 300-g dosage caused significant arrestment of upwind flight. Peak response to synthetics, however, was significantly lower than to female glands. Omitting decyl acetate from the blend did not affect the activity, while omission of any of the three monounsaturated acetates caused a dramatic decrease in response. In the field maximum trap catches were achieved with 1- to 30-g lures. The subtractive assay carried out in the field confirmed the neutrality of decyl acetate and the importance of the three monoenes. Adding 1% of (Z)-8-dodecenyl acetate (earlier reported as an inhibitor) to the four-component mixture decreased the trap catch to about 50%, and increasing the amount of (Z)-8-dodecenyl acetate to 27% decreased the activity further to about 10%. (Z)-8-Dodecenyl acetate also decreased the number of successful flights in the flight tunnel.Schiff., Lepidoptera: Noctuidae.This study was made within the Swedish project Odour Signals for Control of Pest Insects.     

Compounds modifying the activity of two sex attractants for males of the pea moth,Cydia nigricana (F.)

(E)-10-Dodecen-1-yl acetate (E10–12Ac) and (E,E)-8,10-dodecadien-1-ylacetate (E,E8,10–12Ac) are sex attractants for males of the pea moth,Cydia nigricana (F.). Thirty-two structurally related compounds with chain lengths of 9–14 carbon atoms were exposed withE10–12Ac orE,E8,10–12Ac in traps in the field to investigate their influence on the activity of the attractants. Only alchols and acetates unsaturated at C-8, -9, or -10 greatly influenced moth captures. (Z) and (E)-8-dodecen-1-ol were weak synergists forE10–12Ac but no synergists forE,E8,10–12Ac were found. (Z) and (E)-8-dodecen-1-yl acetate and (E,E)-8,10-dodecadien-1-ol inhibited bothE10–12Ac andE,E8,10–12Ac while (E)-10-dodecen-1-ol, 10-dodecyn-1-ol, (Z) and (E)-9-dodecen-1-yl acetate, (Z)-10-dodecen-1-yl acetate, and undecyl acetate inhibited only the former attractant.     

Identification, Synthesis, and Field Evaluation of the Sex Pheromone of the Citrus Fruit Borer Ecdytolopha aurantiana

The sex pheromone of the citrus fruit borer Ecdytolopha aurantiana has been identified by gas chromatography coupled to an electroantennographic detector (GC-EAD). The electron impact mass spectral (EI-MS) fragmentation of the major EAD-active peak gave identifying features for a monounsaturated acetate. Further analyses by chemical ionization mass spectrometry (CI-MS), vapor-phase infrared spectroscopy (GC-IR), along with chemical derivatization (DMDS reaction), led to full characterization of the major component as (E)-8-dodecenyl acetate (E8–12 : Ac). The second constituent was identified as the related alcohol, (E)-8-dodecenol (E8–12 : OH). The two compounds were indistinguishable from the authentic synthetic standards in chemical and EAD analyses. Samples of the two compounds were obtained by a facile synthesis utilizing lithium chemistry. Field tests showed that captures in traps baited with a mixture of E8–12 : Ac and E8–12 : OH at 100 : 1 and 10 : 1 ratios were not significantly different from the catches in traps having two virgin females. Dosage tests showed better performance of traps baited with 1 mg than those with 0.1 mg of the pheromone blend, either in 100 : 1 or 10 : 1 ratio.     

Sex pheromone components isolated from china corn borer,Ostrinia furnacalis guenée (lepidoptera: Pyralidae), (E)- and (Z)-12-tetradecenyl acetates

The sex pheromone components from the corn borer spreading widely in China,Ostrinia furnacalis Guenée, have been identified as (E)-and (Z)-12-tetradecenyl acetates (E andZ12–14 Ac). The ratio ofE isomer toZ isomer was 53 47. Traps containing 1 × 10^–7–1 × 10^–5 g of these compounds captured more males than did live females or their tip extract (3–6 female equivalents). Tetradecyl acetate (14 Ac) was also identified in the tip extract. Its quantity was about 1.8 times the sum of the other two isomers. However, including this compound in its natural ratio in pheromone traps resulted in a decrease in trap catches (P< 0.05).