Evaluation of the Major Female Eurytoma amygdali Sex Pheromone Components, (Z,Z)-6,9-Tricosadiene and (Z,Z)-6,9-Pentacosadiene for Male Attraction in Field Tests

We evaluated the attraction of male almond seed wasp Eurytoma amygdali to the synthetic alkadienes (Z,Z)-6,9-tricosadiene and (Z,Z)-6,9-pentacosadiene and their blend in almond orchards using baited rubber septa attached to cardboard rectangular adhesive traps. The two alkadienes were recently isolated from virgin female whole body extracts and SPME collected volatiles. The alkenes (Z)-9-tricosene, (Z)-9-pentacosene, and (Z)-9-heptacosene, present in female extracts, were also added to the blend of the alkadienes and tested. The alkadienes tested individually attracted males when the traps were baited with doses ranging from 10 to 30 mg/trap. The maximum number of males was attracted to traps baited with 10 mg of a (Z,Z)-6,9-C(23:2):(Z,Z)-6,9-C(25:2) blend at a ratio of 7:3. Results with the three alkenes added to the blend were inconclusive because of low populations. The present study on E. amygdali is the first one reporting attraction of males to synthetic sex pheromone components in field trials for a Eurytomidae species. The synthetic alkadienes blend offers the potential to develop an effective system for monitoring populations of the almond seed wasp in almond orchards.     

(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.     

Enantiomers of (Z,Z)-6,9-Heneicosadien-11-OL: Sex Pheromone Components of Orgyia detrita

(6Z,9Z,11S)-6,9-Heneicosadien-11-ol (Z6Z9-11S-ol-C21) and (6Z,9Z,11R)-6,9-heneicosadien-11-ol (Z6Z9-11R-ol-C21) were identified as major sex pheromone components of female tussock moths, Orgyia detritaGuérin-Méneville (Lepidoptera: Lymantriidae), on the basis of (1) analyses of pheromone gland extracts of female O. detrita by coupled gas chromatographic-electroantennographic detection (GC-EAD) and GC mass spectrometry, and (2) field trapping experiments with synthetic standards. Z6Z9-11S-ol-C21 and Z6Z9-11R-ol-C21 in combination, but not singly, attracted significant numbers of male moths. Racemic Z6Z9-11-ol-C21 was more attractive than the 1:3.5 (R:S) blend ratio found in pheromone gland extracts from female moths. Lower and higher homologues of Z6Z9-11-ol-C21 were also detected in GC-EAD recordings of pheromone extracts, and the racemic compounds enhanced attractiveness of Z6Z9-11-ol-C21 in field experiments. Because of trace amounts of these homologues in extracts, their enantiomeric composition could not be determined. This is the first report of secondary alcohols as pheromone components in the ditrysian (advanced) Lepidoptera.     

Abraxas grossulariata L. (Lepidoptera: Geometridae): Identification of (3Z,6Z,9Z)-3,6,9-heptadecatriene and (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene in the female sex pheromone

(3Z,6Z,9Z)-3,6,9-Heptadecatriene and (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene have been identified in female sex pheromone gland extracts ofAbraxas grossulariata L. (Lepidoptera: Geometridae). The compounds were detected by gas chromatography with electroantennographic detection (GC-EAD) and identified by GC-mass spectrometry (GC-MS). The amounts of hydrocarbon and epoxide were 0.13 and 0.42 ng/female, respectively. These identifications were confirmed by synthesis; the absolute configuration of the epoxide remains to be determined. Another isomeric epoxide, (3Z,6Z)-3,6-cis-9,10-epoxyheptadecadiene, was tentatively identified in small amounts (0.04 ng/female). Racemic (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene elicited the largest electroantennogram response within a series of heptadecadiene and nonadecadiene monoepoxides and the corresponding trienic hydrocarbons and, in field tests, attracted maleA. grossulariata into traps. Addition of 10% (3Z,6Z,9Z)-3,6,9-heptadecatriene to this epoxide enhanced attractiveness; addition of (3Z,6Z)-3,6-cis-9,10-epoxyheptadecadiene had no effect at low proportions while higher proportions caused a reduction in the numbers of males caught.     

Sustained Production of the Labile Pheromone Component, (Z,Z)-6,9-Heneicosadien-11-one, from a Stable Precursor for Monitoring the Whitemarked Tussock Moth

The principal sex pheromone component of the whitemarked tussock moth (WMTM), Orgyia leucostigma, was recently identified as (Z,Z)-6,9-heneicosadien-11-one (Z6Z9-11-one-21Hy). However, it is thermally unstable and quickly degrades under field conditions so that baited traps are effective for only one night. We have developed a solution to this problem that combines two techniques: (1) the use of a stable pheromone precursor, (Z,Z)-6,9-heneicosadien-11-one ethylene ketal, which is hydrolyzed to the dienone by an acidic aqueous solution (2% p-toluenesulfonic acid in 35% aqueous sorbitol), and (2) use of a small, off-the-shelf, autonomous pump (the Med-e-Cell Infu-disk™) to deliver the precursor continuously to a suitable substrate where it is converted rapidly into the attractive dienone pheromone component. The pump and hydrolysis substrate fit inside sticky traps and because generation and release of pheromone is continuous, the instability of the pheromone is not an issue. In electroantennogram bioassays, dose-dependent responses were obtained with 1 to 1000 ng of hydrolyzed ketal on filter paper, but no response was obtained to 1000 ng of the ketal itself. In wind tunnel bioassays, males were attracted to lures emitting the dienone pheromone component generated from 0.1 to 100 ng of the hydrolyzed ketal. Field tests in 2004 and 2005 showed that sticky traps fitted with the pump delivering the ketal (0.1–1 μg/μL in heptane) at 10 μL/hr to a cotton pad soaked with the hydrolyzing solution were attractive to male WMTM. No moths were caught in controls or traps baited with (Z)-6-heneicosen-11-one. An average of 0.51 moths per trap night was caught over an 18-night period in 2005. The results represent a first step toward developing a sensitive and practical monitoring tool for the WMTM by using a ketal precursor of its unstable dienone pheromone component.     

(Z)-10-nonadecenal: A pheromonally active air oxidation product of (Z,Z)-9,19 dienes in yellowheaded spruce sawfly

Each of 10 (Z,Z)-9,19 hydrocarbon dienes (28–37 carbons) found in female yellowheaded spruce sawflies,Pikonema alaskensis (Rohwer), was synthesized and found to be attractive to males by field bioassay. These dienes oxidize slowly in air, major products being aldehydes. One product common to all the dienes, (Z)-10-nonadecenal (Z10–19∶Al), and one from the 29-carbon diene only, (Z)-10-eicosenal, initiated flight and caused upwind anemotaxis in males in a greenhouse bioassay.Z10–19∶Al was incorporated into Hercon® controlled release formulations and was active in the field. The aldehyde could be useful for monitoring sawfly populations.     

(5Z,9Z)-3-alkyl-5-methylindolizidines fromSolenopsis (Diplorhoptrum) species

The alkaloidal venom components of two species of thief ants,Solenopsis (Diplorhoptrum) species AA andS. (Diplorhoptrum)conjurata have been found to contain (5Z,9Z)-3-hexyl-5-methylindolizidine and a mixture of (5Z,9Z)-3-ethyl-5-methylindolizidine andcis-2-methyl-6-nonyl-piperidine,trans-2-methyl-6-nonylpiperidine,cis-2-methyl-6-undecylpiperidine, and hexadecanoic acid.Monomorium pharaonis was similarly investigated and found to contain the indolizidine and pyrrolidines previously described (Ritter et al., 1977b). Both indolizidines were synthesized along with their stereoisomers and separated by preparative gas chromatography. Spectral studies revealed the stereochemistry to be 5Z,9Z in both cases. The stereochemistry of 2-butyl-5-pentylpyrrolidine inM. phaeronis has also been established. Biosynthetic relationships are discussed.     

(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)-4-Tridecenal,a pheromonally active air oxidation product from a series of (Z,Z)-9,13 dienes inMacrocentrus grandii Goidanich (Hymenoptera: Braconidae)

(Z)-4-Tridecenal was identified as a sex pheromone component ofMacrocentrus grandii, a larval parasitoid of the European corn borer. The aldehyde was found to be a common air oxidation product from a series of (Z,Z)-9,13-dienes of 27–33, 35, 37, 39, and 41 carbon atoms in female wasps. Synthetic (Z)-4-tridecenal and (Z,Z)-9,13-heptacosdiene each elicited flight initiation, upwind anemotaxis, casting, landing on the source, walking, wing fanning, and copulatory attempts by male wasps in a wind-tunnel. Field studies demonstrated that both compounds are synergized by a more polar component. Synthetic (E)-4-tridecenal was not attractive.     

(Z,Z)-7,9-Dodecadienyl acetate,sex pheromone ofEpinotia tedella clerck (Lepidoptera: Tortricidae)

(Z,Z)-7,9-dodecadienyl acetate, a reported male attractant for several New World spp. ofEpinotia, was identified as the primary pheromone of femaleE. tedella (European spruce budmoth) through chemical analysis of pheromone gland washes, the electrophysiological study of male antennal receptor types, and field-trapping tests. The washes contained this compound at a level of approximately 0.4 ng per FE, along with a similar amount of the corresponding alcohol, (Z,Z)-7,9-dodecadien-1-ol. Each compound activated its own specialized type of male receptor cell. No traces of stereoisomers or monoenes were found in the washes. In field-trapping tests conducted in stands of Norway spruce in southern Germany, (Z,Z)-7,9-do-decadienyl acetate as a single chemical proved highly attractive to maleE. tedella over a range of lure doses. The corresponding alcohol or aldehyde did not show attractivity; rather, in binary combinations with the primary pheromone, these compounds, and also the (E,Z)-7,9 stereoisomeric acetate, reduced captures. A 101 blend of (E)-9- and (Z)-9-dodecenyl acetates, reported as anE. tedella male attractant, did not reveal significant captures. No otherEpinotia spp. besidesE. tedella responded to the various 7,9-do-decadienyl test baits during this study.     

Linoleic acid metabolism in the red algaLithothamnion corallioides: Biosynthesis of 11(R)-hydroxy-9(Z),12(Z)-octadecadienoic acid

Incubation of [1-¹⁴C]linoleic acid with an enzyme preparation obtained from the red algaLithothamnion corallioides Crouan resulted in the formation of 11-hydroxy-9(Z),12(Z)-octadecadienoic acid as well as smaller amounts of 9-hydroxy-10(E),12(Z)-octadecadienoic acid, 13-hydroxy-9(Z),11(E)-octadecadienoic acid and 11-keto-9(Z),12(Z)-octadecadienoic acid. Steric analysis showed that the 11-hydroxyoctadecadienoic acid had the (R) configuration. The 9- and 13-hydroxyoctadecadienoic acids were not optically pure, but were due to mixtures of 75% (R) and 25% (S) enantiomers (9-hydroxyoctadecadienoate), and 24% (R) and 76% (S) enantiomers (13-hydroxy-octadecadienoate). 11-Hydroxyoctadecadienoic acid was unstable at acidic pH. In acidified water, equal parts of 9(R,S)-hydroxy-10(E),12(Z)-octadecadienoate and 13(R,S)-hydroxy-9(Z),11(E)-octadecadienoate, plus smaller amounts of the corresponding (E),(E) isomers were produced. In aprotic solvents, acid treatment resulted in dehydration and in the formation of equal amounts of 8,10,12- and 9,11,13-octadecatrienoates. The enzymatic conversion of linoleic acid into the hydroxyoctadecadienoic acids and the ketooctadecadienoic acid was oxygen-dependent; however, inhibitor experiments indicated that neither lipoxygenase nor cytochrome P-450 were involved in the conversion. This conclusion was supported by experiments with¹⁸O₂ and H₂ ¹⁸O, which demonstrated that the hydroxyl oxygen of the hydroxy-octadecadienoic acids and the keto oxygen of the 11-ketooctadecadienoic acid were derived from water and not from molecular oxygen. The term “oxylipin” was introduced recently (ref. 1) as an encompassing term for oxygenated compounds which are formed from fatty acids by reaction(s) involving at least one step of mono- or dixoygenase-catalyzed oxygenation.     

Stereospecific synthesis of (Z,Z)-3,5-tetradecadienoic acid,a component ofAttagenus elongatulus (Casey) pheromone

A simple stereospecific synthesis of (Z,Z)-3,5-tetradecadienoic acid is described based upon coupling of 1-decyne and 3-butyn-1-ol to give 3,5-tetradecadiyn-1-ol. Subsequent reduction of the diyne to (Z,Z)-3,5-tetradecadien-1-ol and oxidation of the dienol gave the desired acid.Attagenus elongatulus were strongly attracted to the pure acid.     

(Z,Z)-5,27-Tritriacontadiene: Major sex pheromone ofDrosophila pallidosa (Diptera; Drosophilidae)

A crude cuticular extract from both sexes of 3660 fruit flies (Drosophila pallidosa) was subjected to SiO₂ and AgNO₃/SiO₂ column chromatography, accompanied by bioassay for the sex pheromone activity. After three chromatographic steps, the active fraction was obtained. The main component of the active fraction was determined to be (Z,Z)-5,27-tritriacontadiene [(Z,Z)-5,27-C_33:2, on the basis of gas-liquid chromatographic analysis, chemical derivatization and gas chromatography-mass spectrometry. Synthetic (Z,Z)-5,27-C_33:2 at 5 female equivalents (FE) elicited a clear courtship response with a high courtship index amongD. pallidosa males. Therefore it was concluded that (Z,Z)-5,27-C_33:2 was a major sex pheromone component in this species.     

Field trapping of threeEpinotia species with (Z,Z)-7,9-dodecadienyl acetate (Lepidoptera: Tortricidae)

Field survey of the geometrical isomers of 7,9-dodecadienyl alcohol, acetate, and aldehyde has resulted in attractants and inhibitors for three species of tortricid moths.Epinotia silvertoniensis and an undescribedEpinotia sp. were all attracted to (Z,Z)-7,9-dodecadienyl acetate. AnotherEpinotia sp. was attracted to (Z,Z)-7,9-dodecadienyl acetate and (Z,Z)-7,9-dodecadien-1-ol. Electroantennogram data and inhibition patterns for one of theEpinotia sp. are also reported. In addition,E. criddleana was attracted to lures containing (E)-9-dodecenyl acetate.     

(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.     

Sex pheromone components of three species ofSemiothisa (Geometridae), (Z,Z,Z)-3,6,9-heptadecatriene and two monoepoxydiene analogs

Adult males ofSemiothisa signaria dispuncta (Walker) were attracted to field traps baited with (Z,Z,Z)-3,6,9-octadecatriene and (Z,Z)-6,9-cis-3,4-epoxy-octadecadiene. However, analyses of sex pheromone gland extracts of females of this species by GC-MS and by GC in combination with an electroantennograph detector (GC-EAD) showed the pheromone to be comprised of a mixture of the next lower homologs: (Z,Z,Z)-3,6,9-heptadecatriene and (Z,Z)-6,9-cis-3,4-epoxy-heptadecadiene. Blends of these two C₁₇ compounds were subsequently found to be more attractive to males in the field than the corresponding C₁₈ mixtures. Sex pheromones of two otherSemiothisa species were also found to contain C₁₇ components. (Z,Z,Z)-3,6,9-Heptadecatriene, detected by GC-EAD analysis of a female abdominal tip extract ofS. bicolorata (Fabricius), attracted conspecific males, and this attraction was significantly reduced by additions of (Z,Z)-6,9-cis-3,4-epoxyheptadecadiene, the major pheromone component ofS. signaria dispuncta, to the lure. (Z,Z)-3,9-cis-6,7-Epoxy-heptadecadiene was detected by GC-EAD analysis as the primary male antennal stimulatory component present in abdominal tip extracts ofS. ulsterata (Pearsall), and males of this species were attracted to traps baited with this epoxide. Each of these three C₁₇ compounds constitute previously unknown lepidopteran sex pheromone components. Blends of (Z,Z, Z)-3,6,9-heptadecatriene and (Z,Z)-3,9-cis-6,7-epoxyheptadecadiene attracted males of a fourth species,S. delectata Hulst, but no females of this species were obtained to permit analysis of its sex pheromone. The occurrence of (Z,Z,Z)-3,6,9-heptadecatriene inS. neptaria (Guenee) females was indicated by GC-MS analysis of an abdominal tip extract; however, no males were attracted to any of the fielded mixtures containing this hydrocarbon.     

(Z)-2-(4-氟苯氧基甲基)-2-戊烯-γ-内酯和(Z)-2-(4-氟苯氧基亚甲基)-γ-戊内酯的简便合成

以3－（4－氟苯氧基）丙炔为原料经5步反应合成了（Z）－2－（4－氟苯氧基甲基）－2－戊烯－γ－内酯和（Z）－2－（4－氟苯氧基亚甲基）－γ－戊内酯。合成的关键步骤是在TMSCl/NaI/H2O/CH3CN体系中化合物5－（4－氟苯氧基）－3－戊炔－2－酮一步完成的碘氢化和去共轭反应。     

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.     

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.     

Synthesis of the male stable fly polyene (Z,Z)-1,7,13-pentacosatriene and its geometrical isomers

The four geometrical isomers of 1,7,13-pentacosatriene were synthesized from 1,7-octadiyne. Two of the required isomers were synthesized using known methodology. Hydrogenation of acetylenic linkages were employed to produce predominantly cis alkenes, and alkali metal/amine reduction was used to produce a trans alkene. It was thus possible to produce the (Z,Z) and the (Z,E) isomers. Methods for olefin inversion were then employed to obtain the other two isomers.