(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.     

(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.     

(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.     

Synthesis and field testing of enantiomers of 6Z,9Z-cis-3,4-epoxydienes as sex attractants for geometrid moths

Stereoselective syntheses of chiral C₁₇ to C₂₁ 6Z,9Z-cis-3,4-epoxydienes were developed. Field tests of the enantiomerically enriched epoxides as components of synthetic sex attractant lures were carried out, and those with C₁₇ and C₁₉ chain lengths, particularly, were attractive to male moths of several species. Moths were usually specifically attracted by one of a pair of enantiomers, and the opposite enantiomer could actually be a behavioral antagonist. Males belonging to nine species of Geometridae were captured.Probole amicaria (Herrich-Schäffer) males were taken in traps baited with the mixture (6Z,9Z,3S,4R)-epoxy-nonadecadiene (6Z,9Z,3S,4R-epoxy-19∶H) + 3Z,9Z,6R,7S-epoxy-19∶H + 3Z,6Z,9Z-19∶H(9∶1∶8). Other species responding to the C₁₉ compounds included (attractant components follow in parentheses);Sicya macularia (Harris) (6Z,9Z,3S,4R-epoxy-19∶H + 3Z,6Z,9Z-19∶H),Anavitrinella pampinaria (Guenée) (6Z,9Z-cis-3,4-epoxy-19∶H + 3Z,9Z,6S,7R-epoxy-19∶H), andLycia ursaria (Walker) (6Z,9Z-3S, 4R-epoxy-19∶H + 3Z,6Z,9Z-19∶H). Males of the following species were captured byC ₁₇ epoxides:Itame occiduaria (Packard) (6Z,9Z,3R,4S-epoxy-17∶H + 3Z,6Z,9Z-17∶H),Itame brunneata (Thunberg) (6Z,9Z,3S,4R-epoxy-17∶H),Epelis truncataria (Walker) (both enantiomers of 6Z,9Z-cis-3,4-epoxy-17∶H),Semiothisa ulsterata (Pearsall) (3Z,9Z-6S,7R-epoxy-17∶H), andS. signaria dispuncta (Walker) (3Z,9Z-cis-6,7-epoxy-17∶H + 3Z,6Z,9Z-17∶H). The interactions among enantiomers and regioisomers are discussed as a mechanism by which cross attraction between sympatric species is limited.     

Characterization of Epoxytrienes Derived from (3Z,6Z,9Z)-1,3,6,9-Tetraenes, Sex Pheromone Components of Arctiid Moths and Related Compounds

Cis-9,10-epoxy-(3Z,6Z)-1,3,6-henicosatriene has been identified from a pheromone gland of arctiid species, such as Hyphantria cunea. Since the diversity of lepidopteran species suggests that structurally related compounds of the 9,10-epoxide are also utilized as a sex pheromone components, epoxytrienes derived from (3Z,6Z,9Z)-1,3,6,9-tetraenes with a C₁₉–C₂₁ chain were systematically synthesized and characterized. While 1,2-epoxy-3,6,9-triene was not obtained, peracid oxidation of each tetraene produced a mixture of three cis-epoxides (3,4-epoxy-1,6,9-triene, 6,7-epoxy-1,3,9-triene, and 9,10-epoxy-1,3,6-triene), which were separable by LC as well as GC. Detailed inspection of the mass spectra of the C₁₉–C₂₁ epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 79, M-70, and M-41 for the 3,4-epoxytrienes; m/z 79, 95, 109, and 149 for the 6,7-epoxytrienes; and m/z 79, 106, 120, M-121, and M-107 for the 9,10-epoxytrienes. Resolution of two enantiomers of each C₂₁ epoxytriene was accomplished by HPLC equipped with a chiral column, and analysis of the pheromone extracted from virgin females of H. cunea revealed the 9S,10R configuration of the natural epoxytriene as the same configuration of C₂₁ 9,10-epoxydiene, a main pheromone component of this species. GC-EAD analysis of the optically pure epoxides showed that the antennae of male H. cunea were stimulated more strongly (>100 times) by the (9S,10R)-isomers than the antipodes.     

Evidence for the mitochondrial biosynthesis of 3R-hydroxy-5Z,8Z,11Z,14Z-eicosatetraenoic acid in the yeast Dipodascopsis uninucleata

The biosynthesis of 3R-hydroxy-5Z,8Z,11Z,14Z-eicosatetraenoic acid (3R-HETE) from arachidonic acid (20∶4n−6) by the hyphal-forming yeast, Dipodascopsis uninucleata, in cell-free enzyme extracts required CoASH, ATP, NAD⁺ and Mg²⁺; 3R-HETE was present as the CoA derivative in enzyme extracts and its biosynthesis was associated with mitochondria. Its synthesis was high from arachidonoyl-CoA (15% conversion of the substrate; 22 nmol mg protein⁻¹·h), but significantly higher from trans-2-arachidonoyl-CoA (53 nmol mg protein⁻¹·min). Aspirin, an inhibitor of prostaglandin endoperoxide synthase synthase (cyclooxygenase), did not significantly inhibit 3R-HETE biosynthesis in enzyme extracts, as opposed to antimycin A (46% inhibition). The chirality of 3-HETE was 95% R and 5% S. 3R-HETE has the same chirality as the products of peroxisomal enoyl-CoA hydratases of Neurospora crassa and Saccharomyces cerevisiae; the difference appears to be that in D. uninucleata the R-enantiomers are synthesized in mitochondria. Exogenously supplied eicosapentaenoic acid was converted to 3-hydroxy 5Z,11Z,14Z,17Z-eicosapentaenoic acid by cell-free enzyme extracts though there was no requirement for a 5Z,8Z-diene structure for the biosynthesis of 3-hydroxylated fatty acids as 3-hydroxy-8Z,11Z,14Z, and 3-hydroxy-11Z,14Z,17Z-eicosatrienoic acids were synthesized from the corresponding fatty acids. We found no evidence for the synthesis of the prostaglandins F_2α and F₂.     

Description of sexual behaviors ofDrosophila rajasekari

The courtship behaviors and cuticular hydrocarbons ofDrosophila rajasekari are described. Sexually mature males orient, tap, follow, vibrate their abdomens, extend and vibrate their wings, and attempt copulation during courtship. They perform these behaviors in response to immature and matureD. rajasekari of both sexes, and their courtship activities are facilitated by light. The predominant cuticular hydrocarbon found in both sexes is (Z,Z)-7,11-heptacosadiene (HCD), a compound known to be used as a courtship-stimulating sex pheromone by another fruit fly,D. melanogaster. Therefore, it is not surprising thatD. melanogaster males actively court both males and females from theD. rajasekari stock. However, HCD is apparently not used byD. rajasekari as a courtship-stimulating pheromone since matureD. rajasekari males do not courtD. melanogaster females, which produce large quantities of HCD.     

(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.     

Cuticular hydrocarbons of Drosophila birchii and D. serrata: identification and role in mate choice in D. serrata

The cuticular hydrocarbon compositions of two sympatric species of Australian Drosophila in the montium subgroup of the melanogaster group that use cuticular hydrocarbons in mate recognition have been characterized. Drosophila birchii has 34 components in greater than trace amounts, with a carbon number range of C₂₀ to C₃₃. Drosophila serrata has 21 components above trace level and a carbon number range of C₂₄ to C₃₁. These two species share eight hydrocarbon components, with all but two of them being monoenes. For both species, the (Z)-9-monoenes are the predominant positional isomer. The hydrocarbons of D. birchii are n-alkanes, n-alkenes (Z)-5-, (Z)-7-, (Z)-9-, and (Z)-11-), low to trace levels of homologous (Z,Z)-7,11- and (Z,Z)-9,13-dienes; and trace amounts of (Z,Z)-5,9-C_25:2, a major component of D. serrata. Only one methyl branched hydrocarbon was detected (2-methyl C₂₈), and it occurred at very low levels. The hydrocarbons of D. serrata are dominated by a homologous series of (Z,Z)-5,9-dienes, and notably, are characterized by the apparent absence of n-alkanes. Homologous series of (Z)-5-, (Z)-7-, and (Z)-9-alkenes are also present in D. serrata as well as 2-methyl alkanes. Drosophila serrata females display strong directional mate choice based on male cuticular hydrocarbons and prefer D. serrata males with higher relative abundances of the 2-methyl alkanes, but lower relative abundances of (Z,Z)-5,9-C_24:2 and (Z)-9-C_25:1.     

Olefinic acetates, Δ-9,11–14: OAc and Δ-7,9–12: OAc used as sex pheromone components in three geometrid moths,Idaea aversata,I. straminata,andI. biselata (Geometridae,Lepidoptera)

Pheromone compounds so far identified from most geometrid moths consist of all-Z diene, triene, or tetraene hydrocarbons with chain lengths of C₁₇ to C₂₁, and their monoepoxide derivatives biosynthesized from linoleic and linolenic acids. The present study reports the occurrence of olefinic acetates as sex pheromones in three species of Geometridae. (Z,Z)-9,11-tetradecadienyl acetate and (Z,Z)-7,9-dodecadienyl acetate found in female gland extracts ofIdaea aversata elicited significant responses from conspecific male antennae in gas chromatography with electroantennographic detection (GCEAD). In extracts ofI. straminata, (Z,Z)-7,9-dodecadienyl acetate, (E,Z)-7,9-dodecadienyl acetate, and (Z,Z)-7,9-dodecadienyl acetate were found, and the synthetic compounds elicited strong responses from conspecific male antennae. In the third species,I. biselata, only (Z,Z)-7,9-dodecadienyl acetate was found in the female extracts, and this compound elicited a strong EAD response from the conspecific male antenna. The identities of the pheromone components inI. aversata andI. straminata were further confirmed according to their characteristic ions after GC-MS analyses. Single sensillum recordings fromI. aversata showed two types of pheromone-detecting sensilla present on the male antenna. One type contained two receptor neurons, one of which was specifically tuned to (Z,Z)-9,11-tetradecadienyl acetate, the other to (Z,E)-9,11-tetradecadienyl acetate. A second type contained one neuron responding to (Z,Z)-7,9-dodecadienyl acetate. The two types were clearly different also with respect to external morphology, the former being considerably longer and having a larger base diameter. Also inI. straminata two physiological types of sensilla could be distinguished. One type contained two neurons, one of which responded to (Z,Z)-7,9-dodecadienyl acetate, the other to (Z,E)-9,11-tetradecadienyl acetate. The second type contained one neuron, responding to (Z,Z)-7,9-dodecadienyl acetate. No correlation between external morphology and physiological response of the investigated sensilla was observed inI. straminata. In field tests, a two-component blend containing (Z,Z)-9,11-tetradecadienyl acetate and (Z,Z)-7,9-dodecadienyl acetate in a ratio of 10:1 was attractive to males ofI. aversata. This two-component blend was also attractive to males ofI. straminata, but in a ratio of 1:1. High numbers of maleI. biselata were caught in traps baited with (Z,Z)-7,9-dodecadienyl acetate alone. The incorporation of deuterium labels into pheromone components after topical application of deuterium-labeled palmitic acid confirmed that the pheromone components ofI. aversata could be synthesized from this precursor, as has been previously observed for acetate pheromone components of many other moth species. Our results suggest that an evolutionary reversal back to the production of palmitic acid-derived pheromone components has occurred within the geometrid subfamily Sterrhinae.     

Biosynthesis and PBAN-Regulated Transport of Pheromone Polyenes in the Winter Moth, Operophtera brumata

The trienoic and tetraenoic polyenes, (3Z,6Z,9Z)-3,6,9-nonadecatriene, (3Z,6Z,9Z)-3,6,9-henicosatriene, and (3Z,6Z,9Z)-1,3,6,9-henicosatetraene were found in the abdominal cuticle and pheromone gland of the winter moth Operophtera brumata L. (Lepidoptera: Geometridae), in addition to the previously identified single component sex pheromone (3Z,6Z,9Z)-1,3,6,9-nonadecatetraene. The pheromone biosynthesis activating neuropeptide (PBAN) is involved in the regulation of polyene transport from abdominal cuticle to the pheromone gland. In vivo deuterium labeling experiments showed that (11Z,14Z,17Z)-11,14,17-icosatrienoic acid, the malonate elongation product of linolenic acid, (9Z,12Z,15Z)-9,12,15-octadecatrienoic acid, is used to produce (3Z,6Z,9Z)-3,6,9-nonadecatriene and (3Z,6Z,9Z)-1,3,6,9-nonadecatetraene.     

5,8‐Dihydroxy‐9,12,15(Z,Z,Z)‐Octadecatrienoic Acid Production by Recombinant Cells Expressing Aspergillus nidulans Diol Synthase

Whole cells of recombinant Escherichia coli expressing diol synthase from Aspergillus nidulans produced 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid from α‐linolenic acid via 8‐hydroperoxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid as an intermediate. The optimal conditions for 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid production using whole recombinant cells were exhibited at pH 7.0, 40 °C, and 250 rpm with 40 g/L cells, 12 g/L, α‐linolenic acid, and 5 % (v/v) dimethyl sulfoxide in a 250‐mL baffled flask containing 50 mL reaction solution. Under these conditions, whole recombinant cells produced 9.1 g/L 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid for 100 min, with a conversion yield of 75 % (w/w), a volumetric productivity of 5.5 g/L/h, and specific productivity of 137 mg/g‐cells/h. As an intermediate, 8‐hydroperoxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid was observed at approximately 1.4 g/L after 100 min. With regard to dihydroxy fatty acid production, this is the highest reported volumetric and specific productivities thus far. This is the first report on the biotechnological production of 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid.     

Characterization,synthesis, and behavioral responses to sex attractiveness pheromones of red-sided garter snakes (Thamnophis sirtalis parietalis)

The sex attractiveness pheromone of the red-sided garter snake,Thamnophis sirtalis parietalis, has been characterized as a mixture of 13 long-chain (C₂₉-C₃₇) saturated and monounsaturated methyl ketones. Samples of the major unsaturated ketones in the mixture, (Z)-24-tritriaconten-2-one (7) and (Z)-26-pentatriaconten-2-one (10), and their saturated analogs, 2-tritriacontanone (8) and 2-pentatriacontanone (11) were prepared by unambiguous synthesis. In field bioassay tests, male garter snakes were presented with natural and synthetic pheromone components both individually and as a mixture. Males exhibited courtship behavior to the synthetic compounds approximating the natural blend.     

Unsaturated Cuticular Hydrocarbons Synergize Responses to Sex Attractant Pheromone in the Yellow Peach Moth, Conogethes punctiferalis

Four trienyl hydrocarbons, (Z3, Z6, Z9)-tricosatriene (Z3, Z6, Z9-23:HC), (Z3, Z6, Z9)-pentacosatriene (Z3, Z6, Z9-25:HC), (Z3, Z6, Z9)-heptacosatriene (Z3, Z6, Z9-27:HC), and (Z3, Z6, Z9)-nonacosatriene (Z3, Z6, Z9-29:HC) were identified in a non-polar fraction of the body wax of male and female yellow peach moth, Conogethes punctiferalis. The relative amounts and ratios of these hydrocarbons differed between sexes. In females, the ratios in body wax and pheromone gland extracts were similar, with lesser amounts found in gland extracts. Synergistic effects of these hydrocarbons when added to the known aldehyde pheromone components were assessed in wind tunnel tests. A blend of (E)-10-hexadecenal (E10-16: Ald) and (Z)-10-hexadecenal (Z10-16: Ald) elicited upwind flight and orientation of males to the pheromone source, but arriving males did not remain close to source for very long. Among the hydrocarbons identified, only Z3, Z6, Z9-23:HC enhanced the activity of the aldehyde blend by increasing the time spent close to the source and the number of source contacts. Z3, Z6, Z9-23:HC and (Z9)-heptacosene (Z9-27:HC) also increased close-range responses to the aldehyde blend. The activity of the aldehyde blend plus these two hydrocarbons was similar to that of crude pheromone extract. Positive dose-response relationships between the aldehyde blend and two hydrocarbon mixtures were found. The lowest doses that elicited synergism were 10^?1 female equivalents (of body wax extracts) for the two hydrocarbons, and 10^?2 female equivalents for the total unsaturated hydrocarbon mixture.     

(Z)-11-Eicosen-1-ol, a Major Component of Apis cerana Venom

The unusual venom of Apis cerana contains large oily droplets within an otherwise aqueous secretion. Chemical analysis (GC-MS) revealed that the venom oil consists of (Z)-11-eicosen-1-ol (81.2%), other linear alcohols (7.7%), and linear hydrocarbons (11.1%). The eicosenol is present in extremely large quantities, averaging over 250 μg per insect, and is absent, or present in small quantities, in other parts of the sting apparatus. An investigation of the site of eicosenol storage in A. mellifera showed it to be absent from the venom and to be associated with the setose area where the more volatile components of the alarm pheromone are stored, as previously shown by others. A third honeybee species, A. dorsata, does not to contain the alcohol. The function of eicosenol in A. cerana in not clear, but may serve to mark stung intruders with pheromone or to attract foragers to marked floral resources.     

Synthesis of (Z,Z)-3, 13-octadecadien-1-yl acetate Component of the sex pheromone ofSynanthedon tenuis

The main component of the sex pheromone of the smaller clear wing moth,Synanthedon tenuis, was synthesized. This iterative synthesis uses the carbocupration of acetylene, followed by the alkylation of the (Z)-alkenyl cuprate or by its reaction with ethylene oxide. (Z,Z)-3,13-octadecadien-1-yl acetate, thus obtained, is of 99.8% stereoisomeric purity. An intermediate of the synthesis was (Z)-9-tetradecene-1-yl acetate which is obtained in high yield and 99.9%Z purity.     

A mating stimulant pheromone of the horn fly,Haematobia Irritans (L.): Demonstration of biological activity in separated cuticular components

Preliminary bioassays with the horn fly,Haematobia irritans (L.), suggested that a mating stimulant pheromone was involved in horn fly courtship behavior. Virgin males readily courted live or dead females but rarely courted live males, dead males, or females thoroughly washed with hexane. The bioassay used was the response of virgin males to treated male horn flies. Results indicated that female cuticular hydrocarbons induced male courtship behavior. Specifically, the female paraffin and monoolefin fractions were biologically active when bioassayed alone or in combination. Three synthetic monoolefins previously shown to be the major components in the female monoolefin fraction were active in bioassays. The compoundsZ-5-tricosene,Z-9-pentacosene, andZ-9-heptacosene were each active, but greater male courtship behavior was observed when these three compounds were bioassayed in combination.Diptera: Muscidae.A portion of a dissertation by the first author to the graduate school of the University of Florida in partial fulfillment of the requirements for the PhD degree.Florida Agricultural Experiment Station Journal Series No. 2078.Mention of a proprietary or commercial product does not constitute an endorsement by either the University of Florida or the U.S. Department of Agriculture.     

(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.     

Identification of Conjugated Pentadecadienals as Sex Pheromone Components of the Sphingid Moth, Dolbina tancrei

Homologs of bombykal, (10E,12Z)-10,12-hexadecadienal, have been reported to be sex pheromones or sexual attractants of several species of sphingid moths. In this study, we identified novel bombykal analogs as sex pheromone components from a Japanese sphingid moth, Dolbina tancrei. Staudinger (Sphingidae: Lepidoptera). Sex pheromone gland extracts from calling female moths were subjected to gas chromatography/electroantennograhic detection (GC/EAD), gas chromatography/mass spectrometry (GC/MS), and gas chromatography (GC) analyses. GC/EAD analyses showed two active components in the crude pheromone extracts. GC/MS analysis determined these two components to be pentadecadienals. GC/MS of their MTAD derivatives showed conjugated double bonds at the 9- and 11-positions, indicating 9,11-pentadecadienals. The isomeric configurations of these candidates were determined by comparison of their Kováts retention indices with those of synthetic compounds. Field bioassays with the four isomers of 9,11-pentadecadienal and their mixtures confirmed that the two sex pheromone components of D. tancrei are (9E,11Z)-9,11-pentadecadienal and (9Z,11Z)-9,11-pentadecadienal, with the highest male catches observed for a 90:10 blend. This is the first report of 9,11-pentadecadienals as sex pheromone components in lepidopteran species.