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.     

Simple and economic syntheses of some (Z)-7- and (Z)-9-alkenyl acetates,and of (E,Z)-7,9-dodecadien-1-yl acetate,the sex pheromone of the European grapevine moth,using aleuritic acid as a common starting material

Short syntheses of (Z)-7-dodecen-1-yl acetate, (Z)-7-tetradecen-1-yl acetate, (Z)-9-dodecen-1-yl acetate, and (Z)-9-tetradecen-1-yl acetate from 7-hydroxyheptanal and 9-oxononanoic acid precursors obtained by oxidative cleavage of easily available aleuritic acid are reported. The key step in these syntheses is a stereoselective Wittig reaction between aldehyde and alkyl-phosphonium salt. Wittig-Horner type reaction of 7-hydroxyheptanal and diethyl cyanomethylphosphonate gave the ,-unsaturated nitrile derivative which after protection of the hydroxyl group was reduced to the corresponding aldehyde. Wittig reaction of the latter, followed by acetylation, completed the synthesis of (E,Z)-7,9-dodecadien-1-yl acetate, the sex pheromone of the European grapevine mothLobesia botrana Schiff.     

(3Z,6Z,9Z, 12Z, 15Z)-Pentacosapentaene, a key pheromone component of the fir coneworm moth, Dioryctria abietivorella

The sex pheromone of the fir coneworm moth consists of a blend of (3Z,6Z,9Z,12Z,15Z)-pentacosapentaene and (9Z,11E)-tetradecadienyl acetate. Analogous blends of polyunsaturated, long-chain hydrocarbons with much shorter chain aldehydes or alcohols recently have been discovered in three other moth species in the superfamily Pyraloidea. These combinations of components from two distinct structural classes may represent an important and widespread new pheromone blend motif within the Lepidoptera.     

Role of (Z)- and (E)-11-tetradecenyl acetate pheromone components in the sexual behavior of the (Z) strain of the european corn borer,Ostrinia nubilalis (Lepidoptera: Pyralidae)

A glass tube olfactometer bioassay was used to examine pheromone response of males of the (Z)-pheromone strain ofOstrinia nubilalis (Hubner). The presence of (E)-11-tetradecenyl acetate at the natural ratio to (Z)-11-tetradecenyl acetate (973; ZE) did not consistently elevate wing-fanning, upwind walking, or clasper extrusion over (Z)-11-tetradecenyl acetate alone. This bioassay did not reveal the behavioral role of (E)-11-tetradecenyl acetate.Published as Journal Article No. 10264 of the Michigan State University Agricultural Experiment Station.     

New lepidopteran sex attractants found by systematic field screening of blends containing (Z)-11- and (E)-11-tetradecenal

By screening (Z)-11-tetradecenal and (E)-11-tetradecenal alone, mixed with each other or mixed with corresponding alcohols or acetates, sex attractants were discovered or improved for nine Lepidoptera. Attractants were found forAcleris sparsana, A. tripunctana, Aphelia viburnana (all Tortricidae),Cilix glaucata (Drepanidae), andCosmia trapezina (Noctuidae). The significance of 11-tetradecenals in tortricid sex attractants is discussed.     

(Z,Z)-6,9-heneicosadien-11-one,labile sex pheromone of the whitemarked tussock moth,Orgyia leucostigma

The whitemarked tussock moth (WMTM), Orgyia leucostigma (J. E. Smith), is a major pest of coniferous and deciduous trees in eastern Canada. Chemical identification of its sex pheromone depended primarily on GC-EAD and HPLC analysis, with confirmation of behavioral activity by wind tunnel and field tests. We identified (Z,Z)-6,9-heneicosadien-11-one (Z,Z-6,9-ket) at 4–5 ng/female as the only essential sex pheromone component. Also detected in female extracts were (Z)-6-heneicosen-11-one (Z6-ket) at 2.5 ng/female, (Z,E)-6,8-heneicosadien-11-one (Z,E-6,8-ket) at about 0.5 ng/female, and a trace amount of (Z,E)-6,9-heneicosadien-11-one. Traps containing as little as 1 g of Z,Z-6,9-ket attracted males at low population levels, indicating it is a potent sex attractant. Traps baited with Z6-ket attracted few males, and in wind-tunnel bioassays it was at least 100-fold less attractive to males than Z,Z-6,9-ket. No improvement in trap catch occurred with the addition of Z6-ket in various binary mixtures with Z,Z-6,9-ket, including the female ratio, and a ternary mixture of Z,Z-6,9-ket, Z6-ket, and Z,E-6,8-ket in the 9:5:1 ratio detected in females was no better than Z,Z-6,9-ket alone. We attribute the presence of Z,E-6,8-ket and Z,E-6,9-ket in female extracts to the spontaneous and rapid stereospecific isomerization of Z,Z-6,9-ket at room temperature. Male flight began at sunset but peaked during the second half of the night.     

(Z,Z)-4,7-tridecadien-(S)-2-yl acetate: sex pheromone of Douglas-fir cone gall midge,Contarinia oregonensis

Our objectives were to identify and field test the sex pheromone of female Douglas-fir cone gall midge, Contarinia oregonensis (Diptera: Cecidomyiidae). Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone extract revealed a single compound (A) that elicited responses from male antennae. Hydrogenation of pheromone extract, followed by renewed GC-EAD analysis, revealed a new EAD-active compound with chromatographic characteristics identical to those of tridecan-2-yl acetate on five fused silica columns (DB-5, DB-210, DB-23, SP-1000, and Cyclodex-B). Syntheses, chromatography, and retention index calculations of all possible tridecen-2-yl acetates suggested that the candidate pheromone A was a tridecadien-2-yl acetate with nonconjugated double bonds. Synthetic candidate pheromone component (Z,Z)-4,7-tridecadien-2-yl acetate (Z4Z7) cochromatographed with A on all analytical columns and elicited comparable antennal activity. In GC-EAD analyses that separated the enantiomers (Z,Z)-4,7-tridecadien-(S)-2-yl acetate (2S-Z4Z7) and (Z,Z)-4,7-tridecadien-(R)-2-yl acetate (2R-Z4Z7) with baseline resolution, only 2S-Z4Z7 as a component in a racemic standard or in pheromone extract elicited antennal responses. In Douglas-fir seed orchards, sticky traps baited with 2S-Z4Z7 captured male C. oregonensis, whereas 2R-Z4Z7 was behaviorally benign. Comparable catches of males in traps baited with racemic Z4Z7 (50 g) or virgin female C. oregonensis suggested that synthetic pheromone baits could be developed for monitoring C. oregonensis populations in commercial Douglas-fir seed orchards.     

Female sex pheromone of oriental tobacco budworm,Helicoverpa assulta (Guenee) (Lepidoptera: Noctuidae): Identification and field testing

Analysis of ovipositor washings from virgin femaleHelicoverpa assulta (Guenée) (Lepidoptere: Noctuidae) from Korea by gas chromatography (GC) linked to electroantennography and GC linked to mass spectrometry resulted in the identification of nine compounds, hexadecanal, (Z)-9-hexadecenal, (Z)-11-hexadecenal, hexadecyl acetate, (Z)-9-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, hexadecan-l-ol, (Z)-9-hexadecen-l-ol, and (Z)-11-hexadecen-1-ol. However, ovipositor washings from females from Thailand contained mainly the 16-carbon aldehydes with very small amounts of (Z)-9-hexadecenyl acetate. Field tests conducted in Korea, China, and Thailand indicated that a binary blend of (Z)-9-hexadecenal and (Z)-11-hexadecenal was sufficient for attraction, although the most attractive ratio of compounds varied with location. In Korea a 201 blend of compounds was the most attractive, while in Thailand a 7.51 blend was most attractive. In China both blends of hexadecenal isomers were equally attractive. Addition of the hexadecenyl acetates to the 201 blend of hexadecenals in the ratio of 13.3 increased the trap catch of maleH. assulta compared to lures containing the aldehydes alone in Korea but reduced trap catch in China. Addition of the hexadecenyl acetates to the 7.51 blend of hexadecenals had no significant effect on trap catch in Thailand or China compared to the aldehydes alone. The addition of the 16-carbon alcohols to the aldehydes had a significantly inhibitory effect in all three countries, suggesting they are not pheromone components. Taken together these results indicate thatH. assulta is polymorphic with at least two populations responding to different sex pheromones.     

9,11-Dodecadienyl alcohols,acetates, or aldehydes as synthetic chemical sex attractants for four Lepidoptera:Cosmopterix gemmiferella (Clemens),Dichrorampha simulana (Clemens),Tortricidia testacea (Packard), and anAncylis sp.

Four lepidoptera were lured to field traps containing various combinations of 9,11-dodecadienes with alcohol, acetate, or aldehyde functional groups. All species required two chemical components for best attraction.Cosmopterix gemmiferella was most responsive to a combination of (9Z)-9,11-dodecadienyl acetate and (9E)-9,11-dodecadienyl acetate in 21 ratio;Dichrorampha simulana to (9E)-9,11-dodecadienyl acetate and (9E)-9,11-dodecadien-1-ol in 101 ratio;Tortricidia testacea to (9Z)-9,11-dodecadienal and (9E)-9,11-dodecadienal in 101 ratio; andAncylis sp. to (9Z)-9,11-dodecadienyl acetate and (9Z)-9,11-dodecadien-1-ol in 101 ratio.     

(3Z,6Z,9Z)-Nonadecatriene and enantiomers of (3Z,9Z)-cis-6,7-Epoxy-nonadecadiene as sex attractants for two geometrid and one noctuid moth species

Sex attractants for the geometrid mothsEufidonia convergaria andCaripeta angustiorata, and the noctuid mothRivula propinqualis have been elucidated during field screening of a series of (3Z,6Z,9Z)-triene hydrocarbons (C_17–22), and the racemic and enantiomerically enriched monoepoxydienes derived from those hydrocarbons. Biologically active compounds were identified by a combination of field testing of synthetic standards, electroantennography, and coupled gas chromatography-electroantennogram detection.E. convergaria males were optimally attracted by a 11 blend of (3Z,9Z)-(6S,7R)-epoxy-nonadecadiene (3Z,9Z-6S,7R-epoxy-19H); other abbreviations follow the same system) with (3Z,6Z,9Z)-nonadecatriene (3Z,6Z,9Z-19H). The 6R,7S enantiomer of the epoxide had no apparent biological activity, either as an attractant or as a behavioral antagonist. Male moths also were attracted to blends of the C₁₈ and C₂₀ homologs of the triene and the epoxide. 3Z,6Z,9Z-19H and 3Z,6Z-cis-6,7-epoxy-19H were identified inE. convergaria female pheromone gland extracts. Males of the geometrid moth speciesC. angustiorata were attracted by a 11 blend of 3Z,6Z,9Z-19H and enantiomerically enriched 3Z,9Z-6R,7S-epoxy-19H. Males of the noctuid mothR. propinqualis were attracted by an approximately 101 blend of 3Z,6Z,9Z-19H and enantiomerically enriched 3Z,9Z-6S, 7R-epoxy-19H. The components were synergistic, with neither being attractive alone. The blend ratio was quite specific, as the attractiveness of blends decreased sharply on either side of the optimum ratio.Issued as NRC No. 30266.     

Syntheses of unconjugated (Z,Z)-diolefinic insect pheromones on insoluble polymer supports

A 2% cross-linked styrene-divinylbenzene copolymer containing pendant trityl chloride groups was used as the solid support in the synthesis of (Z, Z)-3,13-octadecadien-1-yl acetate, a component of the sex attractant of the lesser peachtree borer,Synanthedon pictipes, the peachtree borer,Synanthedon exitiosa, and the cherry tree borer,Synanthedon hector. This solid-phase synthesis is compared with a similar synthetic approach in solution. The solid-phase synthesis of (Z, Z)-7,11-hexadecadien-1-yl acetate, a component of the pheromone of the pink bollworm moth,Pectinophora gossypiella is described.     

(Z)-9-tetradecen-1-ol acetate

(Z)-9-Tetradecen-1-ol acetate [(Z)-9-TDA], identified originally as the sex pheromone of the fall armyworm,Spodoptera frugiperda (J.E. Smith), acted as a secondary sex pheromone when it was tested in sticky traps in field tests. Low-level synergism was obtained when 2 and 10% quantities of (Z)-9-TDA were added to 100 g of (Z)-9-dodecen-1-ol acetate, which is now considered the primary sex pheromone.Lepidoptera: Noctuidae.In cooperation with the University of Georgia College of Agriculture Experiment Stations, Coastal Plain Station, Tifton, Georgia 31794.Mention of a proprietary product does not constitute endorsement by the USDA.     

Sex pheromone components of the oblique-banded leafroller,Choristoneura rosaceana in the Okanagan Valley of British Columbia

(Z)-11-Tetradecen-1-yl acetate, (E)-11-tetradecen-1-yl acetate, and (Z)-11-tetradecen-1-ol were previously reported as the sex pheromone in New York strains of the oblique-banded leafroller,Choristoneura rosaceana (Harris), and (E)-11-tetradecen-1-ol was tentatively identified in female tip extracts. For Okanagan Valley strains ofC. rosaceana, an additional component, (Z)-11-tetradecenal, was identified from female tip extracts by split-less capillary gas-liquid chromatography and mass spectroscopy and was strongly stimulatory in electroantennogram studies. In field tests, 3 mg of 96.521.5 (Z)-11-tetradecen-1-yl acetate, (E)-11-tetradecen-1-yl acetate, and (Z)-11-tetradecen-1-ol (containing approx. 1%E isomer) was not as attractive as female-baited traps, and significant numbers of European leafrollerArchips rosanus L. were attracted. The above blend with 1% (Z)-11-tetradecenal added was significantly more attractive than traps baited with femaleC. rosaceana, butA. rosanus males were still attracted. Increased percentages of (Z)-11-tetradecenal up to 4% caused increased catches ofC. rosaceana and decreased catches ofA. rosanus. Low amounts of (E)-11-tetradecen-1-ol and (E)-11-tetradecenal male also contribute to increased specificity of the synthetic pheromone blend toC. rosaceana.Lepidoptera: Tortricidae.Contribution No. 638, Agriculture Canada, Research Station, Summerland, British Columbia, Canada.     

Identification of volatile sex pheromone components released by the southern armyworm,Spodoptera eridania (Cramer)

Analysis of sex pheromone gland extracts and volatile pheromone components collected from the calling female southern armyworm,Spodoptera eridania (Cramer), by high-resolution capillary gas chromatography and mass spectroscopy indicated that a number of 14-carbon mono- and diunsaturated acetates and a monounsaturated 16-carbon acetate were produced. Gland extracts also indicated the presence of (Z)-9-tetradecen-1-ol. However, this compound was not found in collections of volatiles. Field trapping studies indicated that the volatile blend composed of (Z)-9-tetradecen-1-ol acetate (60%), (Z)-9-(E)-12-tetradecadien-1-ol acetate (17%), (Z)-9-(Z)-12-tetradecadien-1-ol acetate (15%), (Z)-9-(E)-11-tetradecadien-1-ol acetate (5%), and (Z)-11-hexadecen-1-ol acetate (3 %) was an effective trap bait for males of this species. The addition of (Z)-9-tetradecen-1-ol to the acetate blends tested resulted in the capture of beet armyworm,S. exigua (Hubner), males which provides further evidence that the alcohol is a pheromone component of this species.     

Identification and field testing of additional components of female sex pheromone of African armyworm,Spodoptera exempta (Lepidoptera: Noctuidae)

Ovipositor washings from virgin femaleSpodoptera exempta (Walker) (Lepidoptera: Noctuidae) were analyzed by high-resolution gas chromatography (GC) linked to a male electroantennogram (EAG). GC retention times of the two major EAG responses observed were consistent with their assignment as (Z)-9-tetradecenyl acetate and (Z,E)-9,12-tetradecadienyl acetate, as previously identified. However, three other EAG responses were also noted that had GC retention times consistent with (Z)-9-tetradecenal, (Z)-9-tetradecen-1-o 1, and (Z)-11-hexadecenyl acetate. The components were present in the ratio of 10051.53.54, respectively. Further analysis of the ovipositor washings by GC linked to a mass spectrometer (GC-MS) confirmed these findings and indicated the presence of a sixth component consistent with (Z)-11-tetradecenyl acetate present at 2 % of the major component. In field tests carried out in Kenya, (Z)-11-hexadecenyl acetate was the only newly identified component to enhance the catch of the original two-component mixture when presented in their natural ratio. The addition of (Z)-9-tetradecen-1-ol reduced catch, while (Z)-9-tetradecenal and (Z)-11-tetradecenyl acetate had no apparent effect.     

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).     

Female sex pheromone of the Yunnan pine caterpillar moth Dendrolimus houi: first (E,Z)-isomers in pheromone components of Dendrolimus spp

The Yunnan pine caterpillar Dendrolimus houi Lajonquière is a serious defoliator of coniferous forests in southwestern China. Gas chromatography–electroantennography (GC–EAG) analyses of extracts of female sex pheromone glands of D. houi moths revealed the presence of three compounds eliciting antennal responses. These were identified as (5E,7Z)-5,7-dodecadien-1-ol (E5,Z7-12:OH), (5E,7Z)-5,7-dodecadien-1-yl acetate (E5,Z7-12:OAc), and (5E,7Z)-5,7-dodecadienal (E5,Z7-12:Ald) by comparison of their GC retention indices, mass spectra, and EAG activities with those of synthetic standards. Average amounts of E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald per calling virgin D. houi female were 14.7 ± 12.9 ng (± SD), 5.8 ± 5.4 ng, and 0.8 ± 1.4 ng, respectively, in a ratio of 100:39.7:5.6. These three components were also collected from the headspace of calling virgin female moths by solid-phase microextraction (SPME). In addition, trace quantities of (Z)-5-dodecen-1-ol (Z5-12:OH), (5Z,7E)-5,7-dodecadien-1-ol (Z5,E7-12:OH), (5E,7E)-5,7-dodecadien-1-ol (E5,E7-12:OH), (5Z,7E)-5,7-dodecadien-1-yl acetate (Z5,E7-12:OAc), (5Z,7Z)-5,7-dodecadien-1-yl acetate (Z5,Z7-12:OAc), and (5E,7E)-5,7-dodecadien-1-yl acetate (E5,E7-12:OAc) were tentatively identified in female pheromone gland extracts by selected ion monitoring GC-MS. Field trapping experiments showed that E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald were essential for attraction of male D. houi moths. Traps baited with a 20:1:1 blend (alcohol/acetate/aldehyde) loaded on gray rubber septa were as effective as traps baited with virgin female moths. The optimum ratio of acetate to aldehyde was 1:1, and this ratio was more critical than the ratio of either compound to the alcohol. This represents the first example of (E,Z)-isomers in pheromone blends of Dendrolimus species.     

(Z)-11-Hexadecenal and (3Z,6Z,9Z)-tricosatriene: sex pheromone components of the red banded mango caterpillar Deanolis sublimbalis

The sex pheromone of the red banded mango caterpillar, Deanolis sublimbalis (Lepidoptera: Crambidae), a serious pest of the mango Mangifera indica (Anacardiaceae) in India and Southeast Asia and a recent invader into northern Australia, has been identified. Three candidate compounds were identified from pheromone gland extracts of female moths, using gas chromatography (GC), GC-electroantennographic detection and GC-mass spectrometric analyses, in conjunction with dimethyldisulfide derivatization. Field bioassays established that both (Z)-11-hexadecenal (Z11-16:Ald) and (3Z,6Z,9Z)-tricosatriene (3Z,6Z,9Z-23:Hy) were required for attraction of male D. sublimbalis moths, and 1,000 μg of a 1:1 mix of Z11-16:Ald and 3Z,6Z,9Z-23:Hy was more attractive to male moths than caged virgin females. However, the binary blend was only attractive when the isomeric purity of the monounsaturated aldehyde was >99%, suggesting that the (E)-isomer was inhibitory. Although (Z)-11-hexadecen-1-ol (Z11-16:OH) was tentatively identified in gland extracts, the addition of this compound to the binary blend did not increase the numbers of moths captured. The pheromone can now be used in integrated pest management strategies. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

(Z)-11-octadecenyl acetate,an aggregation pheromone inDrosophila simulans

Existence of a male-produced pheromone, which attracts both males and females in a wind-tunnel olfactometer, has been demonstrated inDrosophila simulans (Sturtevant). A pheromone component was identified as (Z)-11-octadecenyl acetate (Z11-18: Ac), also known ascis-vaccenyl acetate. The pheromone is synergized by food volatiles. In bioassay ca. 1/1000 of a mature male equivalent of Z11-18: Ac is attractive and activity increases with increased amounts of Z11-18: Ac. Flies do not begin responding to Z11-18: Ac until after they have been away from food for at least 2 hr. Z11-18: Ac is transferred from the male to the female during mating, and the female emits the majority of the transferred Z11-18: Ac within 6 hr after mating.     

Attraction of redbanded leafroller moths,Argyrotaenia velutinana,to blends of (Z)-and (E)-11-tridecenyl acetates

The pheromone ofArgyrotaenia velutinana (Walker) is a 928150 mixture of (Z)-11-, (E)-11-tetradecenyl and dodecyl acetates. An 8515 blend of (Z)-11- and (E)-11-tridecenyl acetates produces a trap catch equivalent to that with the pheromone blend. The sensory input elicited by (Z)-11-tridecenyl acetate appears to substitute for the sensory input of both (Z)-11-tetradecenyl and dodecyl acetates, whereas the input from (E)-11-tridecenyl acetate appears to substitute for that of (E)-11-tetradecenyl acetate. Surprisingly, addition of dodecyl acetate to the tridecenyl acetates mixture decreases trap catches.Lepidoptera: Tortricidae.