3-Hexyl-5-Methylindolizidine Isomers from Thief Ants, Solenopsis (Diplorhoptrum) Species

The venom alkaloids from the workers of nine collections of Solenopsis (Diplorhoptrum) from California contain either (5E,9E)-3-hexyl-5-methylindolizidine (1c) or (5Z,9E)-3-hexyl-5-methylindolizidine (1d) along with cis-2-methyl-6-nonylpiperidine. The structures of these compounds were determined from their mass spectra and by comparison of their GC-FTIR spectra with those of a synthetic mixture. In view of the facts that a third diastereomer of 3-hexyl-5-methylindolizidine had been reported in previous collections of Solenopsis (Diplorhoptrum) queens from Puerto Rico, and that indolizidines along with other ant venom alkaloids are sequestered by amphibians, the determination of species in this difficult group of ants is significant. In particular, the chemotaxonomic value of the stereochemistry of these venom alkaloids is discussed.     

Chemistry of venom alkaloids in someSolenopsis (Diplorhoptrum) species from Puerto Rico

A number of 15-carbon alkaloids have been identified in venom extracts of four Puerto Rican species of ants in the genusSolenopsis (Diplorhoptrum). Workers of a species from El Verde produced thecis andtrans isomers of 2-methyl-6-nonylpiperidine with the latter isomer predominating. The same compounds were identified in queens of a species from Río Grande, but in this species no alkaloids were detected in worker extracts. Workers of aDiplorhoptrum species collected on Mona Island produced primarily atrans-2-methyl-6-(Z-4-nonenyl)piperidine,3, with smaller amounts of thecis isomer, whereas the major compound found in the queens of the same species on Mona Island was (5Z,9Z)-3-hexyl-5-methylindolizidine, identical with the alkaloid produced by queens of a species collected on Cabo Rojo. Surprisingly, workers of the Cabo Rojo species produced (5Z,9Z)- and (5E,9E)-3-butyl-5-propylindolizidine (4 and5, respectively) reported earlier as the 223AB indolizidines from skins of dendrobatid frogs. The possible significance of the qualitative and quantitative differences in the venom alkaloids synthesized by queens and workers is discussed as is the possibility that ants containing such alkaloids may serve as a dietary source for the skin alkaloids used by certain frogs in chemical defense.     

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.     

(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.     

Species discrimination in five species of winter-flying geometrids (Lepidoptera) based on chirality of semiochemicals and flight season

Enantiomer separation of (6Z,9Z)-cis-3,4-epoxynonadecadiene and (3Z,9Z)-cis-6,7-epoxynonadecadiene could be achieved using chiral high-resolution gas chromatography and a cyclodextrin-bond column. (3Z,9Z)-(6R,7S)-Epoxynonadecadiene was identified from ovipositor extracts ofColotois pen-Naria, while inErannis defoliaria the 6S,7R-enantiomer was found. In field trapping tests pure synthetic enantiomers caught only conspecific males of these species. (3Z,6Z,9Z)-Nonadecatriene was found in both species, while the presence of (3Z,6Z,9Z)-heneicosatriene was indicated inC. Pennaria only. A 10103 blend of (3Z,9Z)-(6R,7S)-epoxynonadecadiene, (3Z,6Z,9Z)-heneicosatriene, and (3Z,6Z,9Z)-nonadecatriene was found to be optimal for catchingC. Pennaria, whileE. Defoliaria males were optimally caught by a 11 mixture of (3Z,9Z)-(6S,7R)-epoxynonadecadiene and (3Z,6Z,9Z)-nona-decatriene. (6Z,9Z)-(3S,4R)-Epoxynonadecadiene was identified from ovipositor extracts ofAgriopis (Erannis) aurantiaria. In field tests the pure enantiomer proved to be a highly specific sex attractant for both the late autumn/early winter flyingA. Aurantiaria and the late winter/early spring flyingA. Leucophearia. Males ofAgriopis marginaria, which fly in late winter/early spring, were attracted to (3Z,9Z)-(6S,7R)-epoxynonadecadiene. The addition of (3Z,6Z,9Z)-nonadecatriene to theS,R-enantiomer increased captures. Optimal catches were recorded with a 103 epoxide-hydrocarbon blend. Enantiomer specificity in all species was confirmed in EAG measurements.     

Synthesis and Characterization of Diepoxyalkenes Derived from (3Z,6Z,9Z)-Trienes: Lymantriid Sex Pheromones and Their Candidates

All stereoisomers of three diepoxyalkenes derived from (3Z,6Z,9Z)-trienes with a C₂₁, C₁₉, or C₁₈ straight chain, lymantriid sex pheromones and their candidates, were synthesized by MCPBA oxidation of optically active epoxyalkadienes. Their chromatographic behaviors were examined with GC and LC equipped with achiral and chiral columns. Detailed inspection of the mass spectra of these epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 128, 167, M-87 and M-85 for (Z)-cis-3,4-cis-6,7-diepoxy-9-enes; m/z 111, M-125 and M-69 for (Z)-cis-6,7-cis-9,10-diepoxy-3-enes; and m/z M-125 and M-139 for (Z)-cis-3,4-cis-9,10-diepoxy-6-enes. Mass chromatographic analysis that monitored these fragment ions revealed the existence of a new pheromonal compound with a C₂₁ chain in an extract from virgin females of a lymantriid species, Perina nuda F. The three diepoxyalkenes were converted into the corresponding DMDS adducts, which showed characteristic ions from fragmentation between the two thiomethyl groups, reflecting the position of an original double bond.     

(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.     

(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.     

3Z,6Z,9Z-Trienes and unsaturated epoxides as sex attractants for geometrid moths

Sex attractants for three species of geometrid moths were discovered during field screening of 3Z,6Z,9Z-trienes, and the racemic monoepoxydienes derived therefrom. MaleProbole amicaria moths were attracted to lure blends containing 6Z,9Z-cis-3,4-epoxy-nonadecadiene (6Z,9Z-cis-3,4-epoxy-19H) with 3Z,9Z-cis-6,7-epoxy-19H. 3Z,6Z,9Z-19H was positively identified and 6Z,9Z-cis-3,4-epoxy-19H was tentatively identified in extracts of female pheromone glands by coupled gas chromatography-electroantennogram detection (GC-EAD) and gas chromatography-mass spectrometry (GC-MS).Sicya macularia male moths were attracted by blends of 3Z,6Z,9Z-19H and 6Z,9Z-cis-3,4-epoxy-19H. The attractive response was strongly antagonized by small amounts of 3Z,9Z-cis-6,7-epoxy-19H, or by larger amounts of 3Z,6Z-cis-9,10-epoxy-19H.Lomographa semiclarata male moths were attracted by a variety of lures containing 3Z,6Z,9Z-17H as a major component. 3Z,6Z,9Z-17H was tentatively identified in a female pheromone gland extract by GC-EAD.Issued as NRCC No. 30258.     

Sex attractants for Geometrid and Noctuid moths

Male moths belonging to 17 species of Geometridae and nine species of Noctuidae were captured in traps baited with synthetic chemicals as part of a field screening program. The compounds tested were the C₁₈-C₂₂ homologs of: (1) (3Z,6Z,9Z)-triene hydrocarbons; (2) mixtures containing equal quantities of (3Z,6Z)-cis-9,10-expoxydienes, (3Z,92Z)-cis-6,7-epoxydienes, and (6Z,9Z)-cis-3,4-epoxydienes; (3) (3Z,6Z)-9S,10R-epoxydienes; (4) (3Z,6Z)-9R,10S-epoxydienes; and (5) (3Z,6Z,9Z,11E)-nonadecatetraene. Field captures and electroantennographic assays revealed a high degree of specificity in the responses of many species to the synthetic chemicals. In several species the ability of males to discriminate between the 9S,10R and 9R,10S enantiomers of the monoepoxydiene isomers was clearly shown. Synergists and inhibitors were discovered for several of the reported attractants, some of which were not previously known to have semiochemical activity. The geometrid moths captured includedEpirrhoe sperryi (Herbulot),Mesoleuca ruficillata (Guenée),Triphosa haesitata (Guenée),Metanema inatomaria (Guenée),Prochoerodes transversata (Drury),Cabera erythemaria (Guenée),Synaxis jubararia (Hulst),Dysstroma brunneata ethela (Hulst),Eulithes testata (Linnaeus),Sicya macularia (Harris),Xanthorhoe iduata (Guenée),X. abrasaria aquilonaria (Herrich-Schäffer),X. munitata (Hübner),Itame loricaria (Eversmann),Eupithecia annulata (Hulst),E. rovocastaliata (Packard) andE. satyrata dodata (Taylor). The noctuid moths captured includedBleptina caradrinalis (Guenée),Idia américalis (Guenée),I. aemula (Hübner),Rivula propinqualis (Guenée),Lomanaltes eductalis (Walker),Spargaloma sexpunctata (Grote),Caenurgina distincta (Neumuller),Euclidia cuspidea (Hübner), andZale duplicata (Bethune). Six of the nine noctuid species captured belong to three subfamilies for which sex attractants had not been reported previously. Details for the stereospecific synthesis of (3Z,6Z)-cis-9,10-epoxydienes are also reported.Issued as NRCC No. 24314.     

(6Z,9Z-3R,4S)-Epoxy-heptadecadiene: major sex pheromone component of the larch looper,Semiothisa sexmaculata (Packard) (Lepidoptera: Geometridae)

Gas chromatographic-electroantennographic analysis (GC-EAD) of female larch looper,Semiothisa sexmaculata (Packard), gland extracts revealed two EAD-active compounds. Retention index calculations, GC-mass spectroscopy in selected ion monitoring mode, and GC-EAD analysis of authentic standards identified the compounds as (3Z,6Z,9Z)-heptadecatriene (3Z,6Z,9Z-17H) and (6Z,9Z)-cis-3,4-epoxy-heptadecadiene (6Z,9Z-cis-3,4-epoxy-17H). Chirality determination of the monoepoxydiene in gland extracts was impeded by small quantities, but field experiments indicated that maleS. sexmaculata were most strongly attracted to enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H (69% ee), while maleS. neptaria (Guenée) responded well to various blends of theR,S- and S,R-epoxide enantiomers. Binary combinations of theR,S-epoxide enantiomer with 3Z,6Z,9Z-17H significantly inhibited response by maleS. sexmaculata, but strongly enhanced attraction of sympatric maleS. marmorata Ferguson. Enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H can be used as a trap bait to monitor populations of the larch-defoliatingS. sexmaculata. Whether 6Z,9Z-3R,4S-epoxy-17H serves as single component sex pheromone inS. sexmaculata or small amounts of 6Z,9Z-3S,4R-epoxy-17H synergize or suppress optimal attraction, will be tested as chirally pure monoepoxydienes become available.     

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.     

Porapak-Q collection of pheromone components and isolation of (Z)- and (E)-14-methyl-8-hexadecenal,sex pheromone components,from the females of four species ofTrogoderma (Coleoptera: Dermestidae)

A major sex pheromone component of each of fourTrogoderma species was isolated by aeration of the female beetles and absorption of the volatiles on Porapak-Q. (Z)-14-Methyl-8-hexadecenal was identified as the major component inT. inclusum andT. variabile, and (E)-14-methyl-8-hexadecenal was identified inT. glabrum. Both (Z)- and (E)-14-methyl-8-hexadecenal were found inT. granarium (Khapra beetle), in the ratio 92Z8E. In laboratory bioassays, male beetles exhibited arousal and mating responses to the aldehydes, and could discriminate between the geometric isomers. The daily production of the aldehyde was calculated for each species, and other active components were detected. These aeration-absorption studies contrast with earlier studies on macerated beetles, in which the aldehyde was not detected. The efficacy of the aeration-absorption system for collection of the sex pheromones is also described. The absorbent (Porapak-Q) efficiently collected the active pheromone; only minor amounts of activity were left in the other parts of the system.     

Electrophysiological and chemical analysis of sex pheromone communication system of the mottled umber,Erannis defoliaria (Lepidoptera: Geometridae)

(Z,Z,Z)-3,6,9-nonadecatriene (Z3,Z6,Z9–19Hy) and (Z,Z)-3,9-cis-6,7-epoxy-nonadecadiene (Z3,Z9-cis-6,7-epo-19Hy) were identified in pheromone gland extracts from femaleErannis defoliaria. The two components were found in a 13 ratio, with the main component,Z3,Z9-cis-6,7-epo-19Hy present at an amount of about 1.5 ng per female. The components were identified by means of gas chromatography-mass spectrometry, gas chromatography-electroantennography and gas chromatography-single sensillum recordings. Single sensillum measurements on the male antenna showed two physiological types of sensilla. One type was characterized by a large spike amplitude cell responding toZ3,Z9-cis-6,7-epoxy-19Hy and a small spike amplitude cell responding toZ3,Z6,Z9–19Hy. A second type responded only with a large spike amplitude cell to the epoxide, and this cell was inhibited by the triene. Of the two pheromone components, the epoxide gave the higher response in the EAG tests. Preliminary field tests support the identification of the pheromone components. The epoxide was also found to be present in the extract of the pheromone gland ofColotois pennaria, and males ofC. pennaria andAgriopis marginaria were trapped by the mixture of the identified compounds.     

(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.     

Pheromone specificity inEriocrania semipurpurella (Stephens) andE. sangii (Wood) (Lepidoptera: Eriocraniidae) based on chirality of semiochemicals

The fifth abdominal segment of femaleEriocrania semipurpurella (Stephens) andE. sangii (Wood) contains a pair of exocrine glands. Hexane extracts of this segment were prepared from both species and analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). For both species, the EAD active peaks were identified as nonan-2-one, (Z)-6-nonen-2-one, and (Z)-6-nonen-2-ol by means of mass spectrometry and comparison of retention indices with those of synthetic standards. Enantiomeric separation of chiral alcohols from the female extracts was achieved by gas chromatographic analysis on a cyclodextrin column. InE. semipurpurella, a mixture of (2S,6Z)-nonen-2-ol and (2R,6Z)-nonen-2-ol (2: I) was found, whereas inE. sangii (2S,6Z)-nonen-2-ol was the predominant enantiomer and only traces of theR enantiomer were indicated by the antennal response. In field tests, a blend of the three compounds was not attractive to conspecific males. A subtractive assay showed that the alcohol in various enantiomeric mixtures was the only attractive compound, whereas addition of (Z)-6-nonen-2-one to the alcohol completely inhibited the attraction of both species. A trapping experiment including a wide range of ratios between theR andS enantiomers showed that baits containing 95–100% of theS enantiomer were attractive to maleE. sangii, whereas males ofE. semipurpurella were attracted to all tested ratios of the enantiomers. However, the response profiles of maleE. semipurpurella differed between populations from southern Sweden, south Finland, and the Kola Peninsula in Russia. In south Sweden males were maximally attracted to a racemic mixture of the alcohols. At the Kola PeninsulaE. semipurpurella was attracted to baits containing 95–100% of theR enantiomer. In south Finland all tested ratios between 0 and 100%R enantiomer trappedE. semipurpurella, but the trap catches appeared to be bimodally distributed with peaks around 15 and 70%R enantiomer. The trapping results suggest the existence of pheromone races or sibling species among the specimens identified asE. semipurpurella.Dedicated to Prof. H. J. Bestmann on the occasion of his 70th birthday.     

Identification of Sex Pheromone Components of a New Zealand Geometrid Moth, the Common Forest Looper Pseudocoremia suavis, Reveals a Possible Species Complex

Gas chromatography–electroantennographic detection analysis of sex pheromone gland extracts of the common forest looper Pseudocoremia suavis (Lepidoptera: Geometridae), a polyphagous defoliator of introduced Pinaceae and many New Zealand trees, revealed four compounds that elicited antennal responses. The two major active compounds (6Z)-cis-9,10-epoxynonadec-6-ene and (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene were identified by comparison with known standards. Of the two minor active compounds, one was tentatively identified as (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene, whereas the other could not be identified because of insufficient amounts in extracts. (6Z)-cis-9,10-Epoxynonadec-6-ene, (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene, and (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene were present in P. suavis gland extracts from Eyrewell Forest, a Pinus radiata plantation in the South Island of New Zealand, in a ratio of 35:65:5, respectively. Trapping trials in Eyrewell Forest established that (6Z)-cis-9,10-epoxynonadec-6-ene attracted male P. suavis. However, addition of (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene to the lure at <10% of (6Z)-cis-9,10-epoxynonadec-6-ene reduced capture of male moths, suggesting that one of its enantiomers was acting as a behavioral antagonist. During January–March of 2005, a blend trial involving single, binary, and ternary mixtures of the three components at Eyrewell Forest and at three other sites (two in the South Island and one in the North Island) revealed the existence of a second taxon of P. suavis at the three additional sites that was attracted to lures containing (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene, either singly or in binary and ternary mixtures with (6Z)-cis-9,10-epoxynonadec-6-ene and (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene. This second taxon was not attracted to lures loaded solely with (6Z)-cis-9,10-epoxynonadec-6-ene.     

Synthesis and Biological Characterization of (Z)-9-Heptadecenoic and (Z)-6-Methyl-9-Heptadecenoic Acids: Fatty Acids with Antibiotic Activity Produced by Pseudozyma flocculosa

Difficulties in isolating and purifying antibiotic fatty acids from culture filtrates of Pseudozyma flocculosa, a biocontrol agent against powdery mildew, have been limiting factors in studying the properties and understanding the mode of action of the biocontrol agent. We report a new protocol for synthesizing (Z)-9-heptadecenoic and for the first time synthesis of (Z)-6-methyl-9-heptadecenoic acids, two antibiotic fatty acids produced by P. flocculosa. This allowed reproducible and quantifiable means of assaying biological activity of the molecules. In these bioassays, both molecules exhibited antifungal activity corresponding to their expected potency. These new developments should facilitate further studies aimed at deciphering the ecological properties of P. flocculosa.     

(Z)-10-Heptadecen-2-one and other 2-ketones in the aggregation pheromone blend ofDrosophila martensis,D. buzzatii,andD. serido

(Z)-10-Heptadecen-2-one was identified as the major aggregation pheromone component inDrosophila martensis, D. buzzatii, andD. serido. Aliphatic 2-ketones were not detected in newly eclosed males or in virgin females of any age. The amount of (Z)-10-heptadecen-2-one in the ejaculatory bulb and on the cuticle of males increased with age. Only trace quantities of (Z)-10-heptadecen-2-one were transferred to the female during mating. 2-Tridecanone was found in the ejaculatory bulb and on the cuticle of maleD. martensis andD. buzzatii, but notD. serido. The amount of 2-tridecanone increased with age. Unexpectedly,2-tridecanone inhibited the aggregation activity of (Z)-10-heptadecen-2-one inD. buzzatii. InD. martensis, 2-tridecanone was significantly less attractive than controls but did not decrease the attractiveness of one fly equivalent of (Z)-10-heptadecen-2-one.D. serido males did not have any 2-tridecanone and the activity of (Z)-10-heptadecen-2-one was not diminished inD. serido by the presence of 2-tridecanone.     

Syntheses of pure (9Z, 11Z), (9E, 11E), (9E, 11Z), and (9Z,11E)-9,11-hexadecadienals-possible candidate pheromones

The title compounds were prepared by six different routes, and recommendations are given for the more convenient procedures in laboratory-scale syntheses. Modifications in the literature preparations of the 9E,11E and 9E,11Z isomers are described. Baseline separation of a prepared mixture of all four isomers of the (9Z, 11Z), (9E, 11E), (9E, 11Z), and (9Z, 11E)-9,11-hexadecadienals was achieved using GC methods with standard capillary columns. [¹³C]NMR spectroscopy of the alkene carbon atoms clearly differentiates between theZ,Z, E,E and eitherE,Z orZ,E isomers of the precursor dienols and thus of the dienals.