M. D. Chisholm

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.

Structure-activity relationships in sex attractants for north American noctuid moths

Sex attractants known for 145 species of noctuid moths have many common features both as to chemical constituents and to their relationships in blends. The great majority of constituents are straight-chain (Z)-alkenols, -alkenals, or -alkenyl acetates of even carbon number (10 through 16). The unsaturation is nonterminal in odd-numbered positions (5 through 11). In effective lures, these components are blended in specific ratios and the components in a sex pheromone or sex attractant blend are structurally related by “one-change” steps. This means that any blend component differs from one or more other components by a single structural alteration, such as a change in double bond position, or a change in carbon chain length, or a change in the oxygen function. For the few multicomponent systems known in detail, the central place in the “one-change” framework is occupied by the predominant blend component. Different patterns of occurrence of lure components occur in the subfamilies Acronictinae, Noctuinae, Hadeninae, Cuculliinae, Amphipyrinae, Heliothidinae, Plusiinae, Acontiinae, and Pantheinae, and some subfamilies are as yet without known lures. Some guiding principles for elucidation of blend compositions for unstudied species are presented; these guidelines can also be used in improvement of some synthetic blends of unsatisfactory quality.

Triunsaturated hydrocarbons, sex pheromone components ofCaenurgina erechtea.

Abstract(Z,Z,Z)-3,6,9-Eicosatriene and (Z,Z,Z)-3,6,9-heneicosatriene have been identified as components of the sex pheromone of the noctuid,Caenurgina erechtea (Cramer), the forage looper. Structural assignments were made on the basis of spectroscopic and chromatographic data and were confirmed by comparison with synthetic material. Flight tunnel behavioral studies demonstrated that either component, when tested individually, would elicit wing fanning responses in males; however, mixtures of the two components increased this response and were essential for initiation of upwind flight and landing. In field experiments, traps baited with either component alone captured few or no adult forage looper males while those baited with both components captured several target males.

Novel sex pheromone components from the fall cankerworm moth, Alsophila pometaria

A sex pheromone extract from fall cankerworm moths,Alsophila pometaria, attracted conspecific males in field tests. Four EAG-active components were isolated from the extract and identified by GC-MS, highfield PMR spectroscopy, and microchemical techniques asn-nonadecane (I), (Z,Z,Z)-3,6,9-nonadecatriene (II), (Z,Z,Z,E)-3,6,9,11-nonadecatetraene (III), and (Z,Z,Z,Z)-3,6,9,11-nonadecatetrane (IV). Studies of the behavioral responses of male moths in a flight tunnel to the isolated components showed II, III, and IV were the major components of the sex pheromone. No sex pheromone behavioral responses were observed for I.

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 components of fall cankerworm moth,Alsophila pometaria : Synthesis and field trapping.

Abstract(Z,Z,Z,E)-3,6,9,11-Nonadecatetraene and (Z,Z,Z,Z)-3,6,9,11-nonadecatetraene, sex pheromone components ofAlsophila pometaria, were synthesized by stereoselective Wittig reactions and found to be spectroscopically and chromatographically identical to isolated natural material. Flight-tunnel bioassays and field-trapping experiments confirmed that the two tetraenes together with (Z,Z,Z)-3,6,9-nonadecatriene are sex pheromone components. While traps baited with either tetraene individually captured conspecific males in field-trapping experiments, addition of the triene, which captured no males by itself, to either tetraene resulted in synergistic responses.

Attraction of moth species of Tortricidae, Gelechiidae, Geometridae, Drepanidae, Pyralidae, and Gracillariidae families to field traps baited with conjugated dienes.

Field surveys of a series of conjugated diunsaturated straight-chain primary alcohols, acetates, and aldehydes (dienes), including the 3,5-dode-cadienyl, 8,10-dodecadienyl, 3,5-tetradecadienyl, 8,10-tetradecadienyl, 9,11-tetradecadienyl, and 10,12-tetradecadienyl primary alcohols, acetates, and most aldehydes, and the related monounsaturated straight-chain primary alcohols, acetates, and aldehydes (monoenes), including the 3-dodecadienyl alcohol and acetates, attracted the following species from the title families. Diene attractants have been demonstrated for at least onePhyllonorycter sp.,Chionodes lugubrella (Fabr.),Leptostales ferruminaria (Zell.),Drepana bilineata (Pack.),Pyrausta fodinalis (Led.),Notocelia purpurissatana Heinr.,Phaneta alterana Heinr. Monoene attractants were demonstrated forHedya separatana (Kft.),Cydia fletcherana (Kft.),Barbara mappana Free.,Ancylis burgessiana (Zell.),Ancylis nubeculana Clem.,Evippe prunifoliella Cham.,Phlyctaenia coronata tertialis (Gn.), aChionodes sp., a Gelechiidae sp., and an unidentifiedPhyllonorycter sp. Replicated field experiments showed attraction-inhibition relationships for most species. Electroantennagram data are presented forLeptostales ferruminaria andDrepana bilineata.

Attraction of tortricid moths of subfamily olethreutinae to field traps baited with dodecadienes.

All four geometrical isomers of 7,9- and 8,10-dodecadienes with acetate, alcohol, and aldehyde functional groups were synthesized and field tested. The field survey produced sex attractant lures for 14 insect species. Species in the generaCydia, Grapholita, Eucosma, Pelochrista, Petrova, Phenta, Hedya, and Pseudosciaphila were captured. Defined lures were developed for some of the species captured. Gas chromatographie retention times for all geometrical isomers of 7,9- and 8,10-dodecadienes with acetate, alcohol, and aldehyde functional groups are reported. A study of the isomerization of 8,10-dodecadienyl acetates and aldehydes impregnated in rubber septa is reported.

Synthesis of sex pheromone components of the forest tent caterpillar, Malacosoma disstria (Hubner) and of the western tent caterpillar, Malacosoma californicum (Packard).

All four geometrical isomers of 5,7-dodecadien-1-ol have been stereoselectively synthesized by using Wittig condensation reactions. (5 Z,7E)-5,7-Dodecadien-1-ol and its corresponding aldehyde are components of the sex pheromone of the forest tent caterpillar. (5 E,7 Z)-5,7-Dodecadienal is a component of the pheromone of the western tent caterpillar. These compounds have been successfully tested in the field.

Trace co-attractants in synthetic sex lures for 22 noctuid moths

Trace components contributed significantly to the potency of synthetic sex attractant lures for males of many species of Noctuidae. Improved synthetic blends for 12 moths includingEuxoa ochrogaster andTrichoplusia ni, and new lure blends for 10 moths are described. In every case the trace constituents were structural analogs of the main lure components.