Formate Analogs as Antagonists of the Sex Pheromone of the Honeydew Moth, Cryptoblabes gnidiella: Electrophysiological, Behavioral and Field Evidence

Cryptoblabes gnidiella Milliére (Lepidoptera: Pyralidae) is an economically important exotic pest of vineyards in Southern Brazil and Uruguay. The sex pheromone of C. gnidiella was identified as a mixture of (Z)-11-hexadecenal and (Z)-13-octadecenal, and has been used to monitor populations of this pest in Israel. The development of mating disruption for this species may be hampered by the chemical instability of the natural pheromone components. Therefore, studies on more stable pheromone analogs may provide tools for a control strategy based on behavior-modifying chemicals. We report here the electrophysiological and behavioral responses of C. gnidiella males to (Z)-9-tetradecenyl formate and (Z)-11-hexadecenyl formate, structural analogs of the pheromone components. In gas chromatography-electroantennogram detection (GC-EAD) studies, both analogs elicited responses from C. gnidiella male antennae. Pre-exposure to the formates did not affect the subsequent EAD responses to the natural pheromone components. The formates acted as pheromone antagonists in wind tunnel tests, inhibiting the responses of males toward both synthetic pheromone and calling females. In the field, captures of males in pheromone-baited traps decreased, in a dose-response pattern, when different amount of formates were added to the pheromone. These pheromone antagonists, thus, are potentially useful as mating disruptants for C. gnidiella in commercial vineyards.     

Experiments with a two-component sex attractant of the silver Y moth (Autographa gamma L.), and some evidence for the presence of both components in natural female sex pheromone

(Z)-7-Dodecen-1-yl acetate and (Z)-7-dodecen-1-ol were synthesized and tested on males of the silver Y moth (Autographa gamma L.) for sex attractant activity. The key step of the synthesis was the isomerization of acetylenic alcohol (III) with potassium 3-amino-propylamide. In EAG tests with a series of dodecen-1-yl acetates and alcohols, the highest activity was elicited by these two compounds. In field tests using three different kinds of dispensers, highest catches were achieved with a mixture of (Z)-7-dodecen-1 -yl acetate and (Z)-7-dodecen-1 -ol which contained 1–5% of the alcohol. Some evidence was also found for the presence of both compounds in extracts of the abdominal tip of females. The quantities of these components in the extract was 1.0 ng/female for the acetate, and 1.1 ng/female for the alcohol.     

Sex pheromone chemistry of the female tobacco budworm moth,Heliothis virescens

(Z)-11 -Hexadecenal (77–91%), (Z)-7-hexadecenal (0.1–2%), (Z)-9-hexadecenal (0.3–2%), hexadecanal (3–19%), (Z)-11-hexadecen-1-ol (1–5%), tetradecanal (1–3%), and (Z)-9-tetradecenal (1–3%) were identified from the heptane washes of the ovipositor of femaleHeliothis virescens (F.) females. In field bioassays, a 152-g mixture of these seven compounds deployed in an insect trap exceeded the attractiveness of 4 virgin femaleH. virescens for males and was 5–6 times more attractive than a mixture of (Z)-1 1-hexadecenal and (Z)-9-tetradecenal (virelure) that was previously reported as the sex pheromone of the species. Four of the seven compounds produced byH. virescens females are also produced byH. zea (Boddie). Specificity of pheromonal signals among the two species is ostensibly dependent upon one or more of the three additional compounds [tetradecanal, (Z)-9-tetradecenal, and (Z)-1 1-hexadecen-1-ol] produced by femaleH. virescens.     

Identification of Male Pecan Weevil Pheromone

The pecan weevil, Curculio caryae is a serious economic pest of pecans (Caryae illinoensis). In late summer, the weevil attacks maturing nuts and damages them when making feeding and/or oviposition punctures. The larvae leave the nut and burrow into the soil, remaining there for two to three years before emerging as adults to commence another cycle. This present work has resulted in the identification of the male pecan weevil pheromone as a mixture of four components; I as both the cis and trans isomers of 2-propenyl-1-methyl-cyclobutaneethanol [also identified as (1R,2S)?(+ and ?)-grandisol], II [(Z)-3,3-dimethylcyclohexane-Δ^1,β-ethanol], III [(Z)-3,3-dimethylcyclohexane-Δ^1,α-acetaldehyde], and IV [(E)-3,3-dimethylcyclohexane-Δ^1,α-acetaldehyde]. They are synthesized by the male pecan weevil, but not by the female, in the ratio 7:16:3:3 of I, II, III, and IV, respectively. These same compounds were earlier identified as the pheromone of the male boll weevil, Anthonomus grandis (Boh.), in which they were isolated from frass in the ratio 6:6:1.5:1.5. However, only the (+) isomer of grandisol was synthesized by male boll weevil. In laboratory tests, 80% of female pecan weevils were attracted to a synthetic formulation based on the ratio found in male pecan weevils, while only 28% of the females were attracted to a synthetic formulation based on the ratio found in boll weevil frass. The attraction of males to these synthetic formulations was minimal (14, 4, and 2%, respectively). Live males and their extracts were also attractive to females, but males did not respond to male or females. Preliminary field tests demonstrated that females were attracted to males and the synthetic pecan weevil formulation, but not to the synthetic boll weevil formulation.     

Sex pheromone chemistry of female corn earworm moth,Heliothis zea

Glass open-tubular capillary Chromatographic and combined glass open-tubular capillary chromatographic-mass spectrometric analyses of ovipositor washes of femaleHeliothis zea, chemical characterization, chemical synthesis, and laboratory and field bioassays showed that the ovipositor wash of the species is made up of 90–95% (Z)-11-hexadecenal, 1–2% (Z)-9-hexadecenal, 0.4–2% (Z)-7-hexadecenal, and 2–7% hexadecanal. Stimuli containing a binary mixture of (Z)-11-hexadecenal and (Z)-9-hexadecenal or the binary mixture in combination with any of the other aldehydes identified from the females elicited intense attraction and close-range precopulatory reactions fromH. zea males.Mention of a commercial or proprietary product in this paper does not constitute a recommendation or an endorsement of that product by the U.S. Department of Agriculture.     

Sex pheromone components of the European goat moth,Cossus cossus

Female tip washings of the European goat moth,Cossus cossus L., were found to contain the following compounds that are structurally similar to known pheromone components of Lepidoptera (%): decyl acetate (1.5), (Z)-5-dodecenol (1), (Z)-5-dodecenyl acetate (66), dodecyl acetate (12), (Z)-5-tetradecenyl acetate (14), tetradecyl acetate (4), and hexadecyl acetate (1.5). The washes contained an average of 125 ng of (Z)-5-dodecenyl acetate per female equivalent. EAG responses to nanogram amounts of the identified products indicated that (Z)-5-dodecenyl acetate was the most potent olfactory stimulant followed by (Z)-5-tetradecenyl acetate and (Z)-5-dodecenol, whereas the saturated acetates caused only weak depolarization. A strong EAG response was also recorded for (Z)-3-decenyl acetate, which was not detected in the female tip washings. Field results showed that (Z)-5-dodecenyl acetate was essential for the attraction of the males and that (Z)-3-decenyl acetate improved the attractiveness of (Z)-5-dodecenyl acetate alone or in combination with (Z)-5-tetradecenyl acetate.     

Identification and Field Evaluation of Sex Pheromone Components of the Pear Barkminer Moth, <Emphasis Type="Italic">Spulerina astaurota</Emphasis>

The pear barkminer moth, Spulerina astaurota Meyrick (Gracillariidae: Gracillariinae), is a harmful pest of the Asian-pear tree. Pheromone components of the female were analyzed by gas chromatography (GC) with an electroantennographic (EAG) detector and GC coupled with mass spectrometry. The analyses of a crude pheromone extract and those of a fractionated extract on a Florisil column indicated three EAG-active components, tetradecadien-1-ol, its acetate, and an aldehyde derivative. Characteristic fragment ions in the mass spectra of the dienyl compounds and derivatives with 4-methyl-1,2,4-triazoline-3,5-dione revealed double bonds at the 9- and 11-positions. By comparing the chromatographic behaviors to those of four authentic geometrical isomers, which were synthesized by three different routes starting from 1,8-octanediol or 1,9-nonanediol, the configuration of each natural component was assigned to be 9Z,11Z; i.e., it was concluded that the S. astaurota females secreted (9Z,11Z)-9,11-tetradecadien-1-ol (Z9,Z11-14:OH) as a main pheromone component, and the acetate and aldehyde derivatives (Z9,Z11-14:OAc and Z9,Z11-14:Ald) as minor components. This identification was confirmed by a field evaluation of the synthetic pheromone. While the male moths could be attracted to a lure baited with Z9,Z11-14:OH alone, Z9,Z11-14:OAc showed a strong synergistic effect on the attraction. Among the lures tested, the mixture of alcohol and acetate in a ratio of 7:3 exhibited the strongest attraction. Addition of Z9,Z11-14:Ald in the mixture did not significantly increase the number of males attracted. Furthermore, the field test indicated that some contamination of a geometrical isomer of the alcohol did not impair the activity of the binary mixture with the 9Z,11Z configuration.     

Reexamination of the Female Sex Pheromone of the Sweet Potato Vine Borer Moth: Identification and Field Evaluation of a Tricosatriene

The sweet potato vine borer moth, Omphisa anastomosalis (Pyraloidea: Crambidae), is a serious pest in tropical and subtropical Asia-Pacific regions. In previous work using a population from Okinawa, Japan, (10E,14E)-10,14-hexadecadienal (E10,E14-16:Ald) was identified as the major pheromone component, with hexadecanal, (E)-10-hexadecenal, and (E)-14-hexadecenal as minor components. However, traps baited with the synthetic compounds were less effective at attracting males in the field than those baited with virgin females. While Pyraloidea females usually produce only Type I pheromone components (unsaturated fatty alcohols and their derivatives), the pheromones of some Pyraloidea species have been shown to involve a combination of both Type I and Type II components (unsaturated hydrocarbons and their epoxides). We examined an extract of the pheromone glands of female O. anastomosalis from Vietnam by gas chromatography coupled to mass spectrometry and detected (3Z,6Z,9Z)-3,6,9-tricosatriene (Z3,Z6,Z9-23:H) in addition to the compounds identified previously. All four isomers of 10,14–16:Ald were synthesized. A mixture of synthetic E10,E14-16:Ald and Z3,Z6,Z9-23:H in a ratio of 1:0.2–1:2 was attractive to male moths in Vietnam, indicating the strong synergistic effect of the Type II compound. Addition of the other minor pheromone components to the binary blend did not increase the number of male moths captured. Combinations of Z3,Z6,Z9-23:H with the other three geometrical isomers of E10,E14-16:Ald attracted no males, further substantiating the 10E,14E configuration of the natural diene component. E10,E14-16:Ald mixed with other polyunsaturated hydrocarbons showed that mixtures that included a C₂₁ triene, a C₂₂ triene, or a C₂₃ pentaene attracted as many males as did the mixture with Z3,Z6,Z9-23:H. The identification of a highly attractive sex pheromone will help in developing efficient strategies for monitoring and control of O. anastomosalis populations in sweet potato fields.     

Sex pheromone differences in populations of the brownheaded leafroller,Ctenopseustis obliquana

Ctenopseustis obliquana females collected from Christchurch were found to produce a mixture of (Z)-5-tetradecenyl acetate and tetradecyl acetate in their sex pheromone gland, in contrast toC. obliquana from Auckland which produce an 80∶20 mixture of (Z)-8-tetradecenyl acetate and (Z)-5-tetradecenyl acetate. This identification has been made on the basis of instrumental and chemical analyses. Antennae of maleC. obliquana from Christchurch gave a maximal electroantennogram response to (Z)-5-tetradecenyl acetate. A field trapping program in Christchurch using combinations of synthetic (Z)-5-tetradecenyl acetate and tetradecyl acetate caughtCtenopseustis males equally well if the latter chemical was present or absent. No males were caught in traps baited with the Auckland-type pheromone. In Alexandra,Ctenopseustis males were caught in traps baited with Auckland-type pheromone and not in traps baited with Christchurch-type pheromone. This phenomenon is ascribed to the existence of sibling species within the describedC. obliquana.     

Field trapping of diamondback mothPlutella xylostella using an improved four-component sex attractant blend

In addition to three known sex lure components [(Z)-11-hexadecenyl acetate, (Z)-11-hexadecenal, and (Z)-11-hexadecenol], (Z)-9-tetradecenyl acetate was field-proven as a trace coattractant for malePlutella xylostella, with an optimal content below 0.01% in blends. This potent four-component lure for diamondback males also attractedCrymodes devastator males, and in this respect is not different in its attractancy from virgin diamondback females. Replacement of (Z)-9-tetradecenyl acetate in the four component lure with (Z)-9-tetradecen-1-ol, at the level of 10% of the total lure mixture, did not alter its attractancy for diamondback males, but it did inhibit attraction ofCrymodes devastator. The status of biologically active components as possible sex pheromones or para-pheromones is discussed.     

Sex pheromone of blackheaded fireworm,Rhopobota naevana (Lepidoptera: Tortricidae), a pest of cranberry

Splitless capillary gas chromatography indicated the presence of (Z)- and (E)-11-tetradecenyl acetate and (Z)-11-tetradecenyl alcohol in the washes of female abdominal tips of the blackheaded fireworm,Rhopobota naevana (Hubner). Gas chromatography combined with mass spectroscopy confirmed the presence of tetradecenyl acetate in extracts of female tips. The low levels observed in these extracts (< 1 ng/female equivalent), prevented further chemical and spectroscopic identification. These materials were found to be stimulatory at low levels in electroantennogram studies. A combination of 9 g of (Z)-11-tetradecenyl acetate and 3 g of (Z)-11-tetradecenyl alcohol on rubber septa in wing traps provided an effective attractant. (Z)-9-Dodecenyl acetate, a previously reported attractant, did not significantly increase field trapping catches when added to the binary mixture, but was found to enhance trap catches when added to each of the primary components.     

Female-produced sexual pheromone ofSceliodes cordalis (Lepidoptera: Pyralidae)

(E)-11-Hexadecen-1-yl acetate and (E)-11-hexadecen-1-ol were identified in extracts from the abdominal pheromone gland of femaleSceliodes cordalis and in a 1∶1 ratio acted as a potent field attractant for males. Sustained upwind flight by males to this mixture in a wind tunnel confirmed the identity of these compounds as major components of the natural sex pheromone of this species. The synthetic pheromone was used to define the annual limits of male flight activity. In the presence of 1–10 μg of pheromone per liter of air, the mating rate of laboratory populations was halved. TheZ isomers of both pheromone components decreased the numbers of males captured in traps baited with virgin females in the field and inhibited upwind flight in the wind tunnel. The attraction of males ofMnesictena flavidalis to virgin females ofS. cordalis and synthetic mixtures was demonstrated to be due to the acetate component alone. MaleEudonia sp. nrlinealis were captured by (Z)-11-hexadecen-1-yl acetate.     

Sex pheromone components of the giant looper,Boarmia selenaria schiff. (Lepidoptera: Geometridae): Identification,synthesis, electrophysiological evaluation,and behavioral activity

(Z,Z)-6,9-cis-(3S,4R)-Epoxynonadecadiene9a and (Z,Z,Z)-3,6,9-nonadecatriene have been identified as sex pheromone components in female ovipositor extracts and effluvia of the geometridBoarmia selenaria. The identification was based on relative retention times on gas chromatographic columns, GC-MS, chemical enantioselective syntheses, EAG, wind-tunnel behavioral experiments, and field tests. A single female ovipositor extract contained an average of 42 ng of (Z,Z)-6,9-cis-3,4-epoxynonadecadiene and 2 ng of (Z,Z,Z)-3,6,9-nonadecatriene.EAG, wind-tunnel behavioral studies, and field tests demonstrated that maleB. selenaria exhibit preferential attraction for the (3S,4R)-enantiomer of (Z,Z)-6,9-cis-3,4-epoxynonadecadiene. Only in effluvia and ovipositor extracts of calling females was (Z,Z)-6,9-cis- 3,4-epoxynonadecadiene detected, whereas relatively high amounts of (Z,Z,Z)-3,6,9-nonadecatriene were found in noncalling females. Wind-tunnel behavioral studies showed that (Z,Z,Z)-3,6,9-nonadecatriene did not elicit any response in the males, and when tested in combination with a mixture of monoepoxynonadecadienes, (Z,Z,Z)-3,6,9-nonadecatriene decreased the observed behavioral responses. A possible precursor role for (Z,Z,Z)-3,6,9-nonadecatriene in the pheromonal system is discussed.     

Hydrocarbon components of the yellowheaded spruce sawfly sex pheromone

The primary sex pheromone of the yellowheaded spruce sawfly,Pikonema alaskensis (Rohwer) (Hymenoptera: Tenthredinidae), was found to include a series of straight-chain hydrocarbon dienes, all with the double bonds in the 9 and 19 positions and all with the (Z, Z) configuration. The major components, of 29, 31, 33, 35, and 37 carbon atoms, were synthesized. In the field and the greenhouse, the synthetic dienes were far above control levels in activity but, at least during the first hours of bioassay, were somewhat less active than the female-derived materials on a weight basis. In the field, a mixture of all five synthetic dienes, in the proportions found in the females, was more attractive than any single one, on a mole basis. In addition, (Z, Z)-9,19 dienes of 28, 30, 32, 34, 36, 38, and 39 carbons have been detected in females in minor amounts. The first five were bioassayed, and each was found to be similar in activity to the 35-carbon component when compared on a weight basis. The synthetic dienes, while active by themselves, were strongly synergized by two, more polar, Florisil fractions derived from females. Experimental design considerations are discussed.     

Chemical Identification, Emission Pattern and Function of Male-Specific Pheromones Released by a Rarely Swarming Locust, Schistocerca americana

Pheromones serve key functions in the biology of swarming locusts. However, research has focused largely on the mass-swarming desert locust, Schistocerca gregaria. We extended these investigations to the pheromonal profile of the rarely swarming American bird grasshopper, S. americana (Drury). The headspace of mature gregarious S. americana males contained three characteristic electroantennogram-active components: (Z)-3-nonen-1-ol, (Z)-2-octen-1-ol, and nonanal. These substances were accompanied by aromatics such as phenol that are also released by females and immatures. Male-specific pheromone components were released independently from epidermal gland cells, with the highest emission rate being for (Z)-3-nonen-1-ol from the abdomen and legs. The emission of the major compound, (Z)-3-nonen-1-ol, is stress-sensitive, and coincides with sexual maturity and crowding. The emission pattern strongly supports a role of (Z)-3-nonen-1-ol in the reproductive biology of S. americana. The pheromone is involved in courtship-inhibition and is used as mate assessment pheromone in cryptic female choice. In double mating experiments, females choose sperm of males with high (Z)-3-nonen-1-ol emission. Furthermore the pheromone accelerated maturation of immature adults and supports synchronization of sexual development.     

Identification of an attractant for the caneborerSesamia grisescens walker (Lepidoptera: Noctuidae)

The composition of the sex pheromone ofSesamia grisescens was investigated using gas chromatography, electroantennograms, and field trapping. (Z)-11-Hexadecenyl acetate and (Z)-11-hexadecenol were identified in field tests as the major attractants. Trapping trials identified a 3:2 blend of these compounds as the most effective bait. Gas chromatography indicated the presence of hexadecyl acetate. (Z)-9-hexadecenyl acetate, (Z)-9-hexadecenol, and (E)-11-hexadecenyl acetate in the pheromone gland, but these compounds had no significant effect on trap catches when added to the major components. Traps baited with the major components in a 1:1 ratio caught more male moths than traps baited with virgin females.     

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     

Identification of sex pheromone components of the female driedfruit moth,Vitula edmandsae serratilineella,and a blend for attraction of male moths

Sixteen pheromone-like compounds were identified in abdomen tip washes and excised abdomen tip extracts of calling females of driedfruit moth,Vitula edmandsae serratilineella Ragonot. Identifications were by high-resolution gas chromatography-mass spectrometry, and gas chromatography with flame ionization and electroantennographic detectors. Male moths were attracted to a blend of (Z)-9,(E)-12-tetradecadienol and (Z)-9,(E)-12-tetradecadienal in a ratio of 100∶1 at 500 μg/rubber septum dispenser, which is recommended for monitoring purposes. Low concentrations of (Z)-9-tetradecenol (0.5%) and (Z)-9-tetradecenal (0.1%) may be beneficial for the attraction of males, but 1–2% of (E)-9,(E)-12- or (Z)-9,(Z)-12-tetradecadienol, or (Z)-9,(E)-12-tetradecadienyl acetate inhibited their attraction. Gravid female moths were attracted to traps that captured large numbers of males. Females may be attracted to male hairpencil or forewing gland secretions emitted near the traps or that accumulate in the traps.     

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.     

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.