Sex pheromone chemistry of the western spruce budwormChoristoneura occidentalis Free

SCOT capillary Chromatographic and SCOT capillary chromatographic-mass spectrometic analyses of gland washes and effluvia of virgin femaleChoristoneura occidentalis Free, have been conducted with both a diapausing and nondiapausing strain of this insect. The following compounds were identified in gland washes and effluvia in both strains:E andZ11–14Ald,E andZ11–14Ac,E andZ11–14OH and 14Ald, 14Ac, and 14OH. The average aldehyde: acetate: alcohol ratio found by analysis of single glands by virgin females (nondiapausing strain) was 170.73. Analysis of virgin female effluvia gave this ratio as 1038 (diapausing strain: %Z=8, 11, 15, respectively) and 1036 (nondiapausing strain: %Z=8, 11, 12, respectively). The saturated components were generally 1–2% of theE isomer in each case. Comparisons of EAG responses of bothC. occidentalis andC. fumiferana toE11–14Ald,E11–14Ac andE11–14OH were made. Correlations with both laboratory and field data previously published were also made betweenC. fumiferana andC. occidentalis.Lepidoptera: Tortricidae.     

Blackheaded fireworm: Laboratory and field studies of its sex pheromone

Electroantennogram (EAG) responses of maleRhopobota naevana (Hübner), the blackheaded fireworm, to all of the monoene straightchain 12- and 14-carbon alcohols and acetates implicated (Z)-11-tetradecenl-1-ol (Z11–14OH) and its acetate (Z11–14Ac) as sex pheromone components.Z11–14Ac produced the strongest EAG response of all compounds tested. Gas chromatography-mass spectrometry (GC-MS) analysis of extract of female sex pheromone glands (SPG) confirmed the presence ofZ11–14OH (125 pg/female) andZ11–14Ac (600 pg/female) (all other monoenes had different retention times). In field tests, traps baited withZ11–14OH alone captured males, but traps baited withZ11–14Ac alone did not. Traps baited with a combination ofZ11–14OH andZ11–14Ac in various ratios did not produce better trap catches thanZ11–14OH alone. (Z)-9-Dodecen-1-ol acetate (Z9–12Ac), reported by others to be a field attractant, did not produce trap catch in our tests, but in combination withZ11–14 OH (982 in septa corresponding to 95:5 in vapor,Z11–14OH toZ9–12AC) produced a sevenfold increase in catch overZ11–14OH alone. IfZ9–12AC had been present in extract of SPG at 2–5% ofZ11–14OH, it would not have been detected in our GC-MS experiment. Rhopobota naevana (Hübner) Lepidoptera: Tortricidae: Olethreutinae.     

Sex pheromone components of female smaller tea tortrix moth,Adoxophyes sp. (Lepidoptera: Tortricidae) in Taiwan

(Z)-11-Teiradecenyl acetate (Z11-14: Ac) and (Z)-9-tetrade-cenyl acetate (Z9–14: Ac) were isolated as major sex pheromone components from the female tips of the smaller tea tortrix moth,Adoxophyes sp., in Taiwan. The average amount ofZ11- andZ9–14: Ac in each female gland was 24.9 and 14.1 ng, in a ratio of 6436, respectively. When compared to a closely related Japanese strain, which used theZ9-14: Ac,Z11-14 Ac,E11–14:Ac, 10-Me-12:Ac four-component system (in a ratio of 633142), the Taiwan formulation of two components caught significantly more Taiwan males than the Japanese formulation of four components.     

Sex pheromone of aPlanotortrix excessana sibling species and reinvestigation of related species

The sex pheromone of aPlanotortrix excessana sibling species was investigated. Females were found to produce eight potential pheromone components: dodecyl acetate, tetradecyl acetate (14OAc). (Z)-5-tetradecenyl acetate (Z5-14OAc), (Z)-7-tetradecenyl acetate (Z7-14OAc), (Z)-9-tetradecenyl acetate, hexadecyl acetate, (Z)-7-hexadecenyl acetate, and (Z)-9-hexadecenyl acetate. When these compounds were bioassayed using field-trapping and wind-tunnel techniques, only 14OAc,Z5-14OAc, andZ7-14OAc were found to be behaviorally active. The sex pheromone glands of females of other species including,Planotortrix MBS,Planotortrix M,P. notophaea, Ctenopseustis servana, and aC. obliquana sibling species, were also found to containZ5-14OAc orZ7-14OAc, singly or in combination. In the case ofPlanotortrix M, the addition ofZ7-14OAc to the previously identified sex pheromone blend ofZ5-14OAc and 14OAc was found to increase trap captures of male moths of this species. Thus in these New Zealand species (and in some Australian species),Z5-14OAc andZ7-14OAc appear to be utilized in combination in pheromonal communication just as (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate are used by many species of Holarctic Tortricidae in the tribe Archipini.Lepidoptera: Tortricidae: Tortricinae.     

Sex pheromone ofAdoxophyes orana: Additional components and variability in ratio of (Z)-9- and (Z)-11-tetradecenyl acetate

Twelve products related to the sex pheromone main components (Z)-9- and (Z)-11-tetradecenyl acetate (Z9–14Ac andZ11–14Ac, respectively), were identified in female pheromone gland extracts of the laboratory-reared summerfruit tortrix moth,Adoxophyes orana F.v R. These are the geometric isomers and the alcohols of the main components, (Z)-9-dodecenyl acetate, (Z)-11-hexadecenyl acetate, and saturated acetates of 12–22 carbons. The ratio ofZ9–14Ac toZ11–14Ac in individuals varied from 3.51 to 111 with an average of 6.2; their total added up to 462 ng/female with an average of 182 ng for 2- to 7-day-old individuals. No qualitative or quantitative differences were observed between laboratory and field insects.Z9–14Ac,Z11–14Ac and the corresponding alcohols were also found in female effluvia. Addition of either of the two alcohols to a blend of the two acetates augmented trap catch in the field. The same was true for (Z)-9,(E)-12-tetradecadienyl acetate which was not detected in gland extracts.     

Effects of dodecyl acetate andZ-10-tridecenyl acetate on attraction ofEupoecilia ambiguella males to the main sex pheromone component,Z-9-Dodecenyl acetate

Attraction ofE. ambiguella males toZ-9-dodecenyl acetate (Z9-12Ac), alone and in combination with dodecyl acetate (12Ac) orZ-10-tridecenyl acetate (Z10-13Ac) was tested in both wind-tunnel and field experiments. In the laboratory, response toZ9-12Ac reached a distinct dosage optimum at which attraction was nearly as good as to live females. Addition of 12Ac, a minor component of female glands and effluvia, had no effect at low doses ofZ9-12Ac and only marginally improved attraction at the optimum. However, inclusion of 12Ac with an overdose ofZ9-12 Ac fully restored activity. In the field,Z9-12Ac alone was not very attractive at any dose; catches markedly increased by adding 12Ac and climbed with increasing dose of each compound up to 10 mg. Optimum ratio ofZ9-12Ac to 12Ac was 11 to 15. Another compound,Z10-13Ac, had the same effect as 12Ac in the laboratory and the field but was effective at a lower dose. In the field, inclusion of the synergist permits use of high cap loads to attract more males, perhaps from greater distances.     

Aggregation pheromone characterization and comparison inDrosophila ananassae andDrosophila bipectinata

(Z)-11-Octadecenyl acetate (Z11–18Ac) and (Z)-11-eicosenyl acetate (Z11–20Ac) were identified as the aggregation pheromones ofDrosophila ananassae, andZ11–20Ac was identified as the aggregation pheromone ofDrosophila bipectinata. Z11–18Ac andZ11–20Ac were not attractive alone; however, in combination with fermenting food odors, the acetates attracted flies of both sexes in a wind-tunnel olfactometer. The pheromones were present in the ejaculatory bulb of sexually mature male flies and transferred to the female during mating. MaleD. bipectinata released little if anyZ11–20Ac to the food; however, recently mated females releasedZ11–20Ac to the surrounding surfaces in just a few hours after mating.D. ananassae males, on the other hand, appeared to release moreZ11–18Ac andZ11–20Ac to the surroundings than mated females. AlthoughD. bipectinata males had noZ11–18Ac, flies were as attracted toZ11–18Ac as to an equal quantity ofZ11–20Ac.D. ananassae were attracted toZ11–18Ac but not toZ11–16Ac orZ11–20Ac. However,Z11–20Ac in combination withZ11–18Ac was significantly more attractive thanZ11–18Ac alone.     

A four-component pheromone blend for optimum attraction of redbacked cutworm males,Euxoa ochrogaster (Guenée)

Four acetates,Z-5-decenyl acetate,Z-5-,Z-7-, andZ-9-dodecenyl acetates, in microgram ratios of 120021 or 120062 were excellent, specific sex pheromone blends for capturing male redbacked cutworm moths in cone traps. Blends in ratios of 120021 and 220021 at 1000 g/ rubber septum dispenser remained highly effective for 6 weeks under field conditions. The essential minor components,Z-5-decenyl,Z-7-, andZ-9-dodecenyl acetates, became inhibitory at concentrations of about 10% in the blends, and this may be an important general phenomenon in lepidopteran pheromones. Blends involving a parapheromone,Z-5-undecenyl acetate, withZ-5-,Z-7-, andZ-9-dodecenyl acetate, in microgram ratios of 820021 or 2020062 were also excellent specific attractants for this species. TheZ-8-dodecenyl acetate had no obvious effect on the attraction of the redbacked cutworm males.     

Sex pheromone of the chokecherry leafroller moth,Sparganothis directana

(E)-9,11-Dodecadienyl acetate and (Z)-9,11-dodecadienyl acetate in conjunction with (E)-11-tetradecenyl acetate and (Z)-11-tetradecenyl acetate were found to comprise the sex pheromone ofSparganothis directana, based on chemical analysis, electroantennogram tests, and field trapping. (E)-9-Dodecenyl acetate and (Z)-9-dodecenyl acetate were also found in gland extracts but did not influence trap catches. The relative amounts of these compounds in the gland were 3521928 106, in the order named. Only (E)-9,1 1-dodecadienyl acetate, (E)-11-tetradecenyl acetate, and (Z)-11-tetradecenyl acetate were required for attraction of males to traps, dispensed in the relative amounts 501238, respectively.Lepidoptera: Tortricidae.Supported by National Science Foundation grant PCM 78-13241.     

Sex pheromone components of corn stalk borerSesamia nonagriodes (Lef.) isolation,identification, and field tests

Z-11-Hexadecenyl acetate (Z11–16OAc), dodecyl acetate (12OAc),Z-11-hexadecenal (Z11–16Aid), andZ-11-hexadecenol (Z11– 16OH), were found in pheromone gland extracts of femaleSesamia nonagriodes (Lef.) [Lepidoptera: Noctuidae]. These four components were also present in airborne volatiles collected from calling virgin females in a 651889 ratio. Hexadecyl acetate (16OAc) was also detected but found to be inactive. The identification was based on multicolumn GC analysis, mass spectrometry, and field activity.Z11–16OAc is the major sex pheromone component; the addition of the secondary components individually decreased male captures. The blend of the four synthetic components in 691588 ratio was highly attractive to males; 200 g per trap was the most effective concentration in field tests.Lepidoptera: Noctuidae     

Sex pheromone components of the obliquebanded leafroller moth,Choristoneura rosaceana

Previously, (Z)-11-tetradecen-1-yl acetate was reported as the sex pheromone of the obliquebanded leafroller,Choristoneura rosaceana (Harris). A mixture of 92% (Z)-11-tetradecen-1-yl acetate and 8% (E)-tetradecen-1-yl acetate has been reported as an attractant for this insect. (E)-11-tetradecen-1-yl acetate and (Z)-11-tetradecen-1-ol have now been isolated and identified from female tip extracts and shown to be behaviorally active; in addition, there is some evidence for the presence of (E)-11-tetradecen-1-ol in these extracts. TheZE ratio for both the acetates and the alcohols in these tip extracts was about 982; the proportion of alcohols was rather variable, but the acetates always predominated. Maximum trap catches fn the field during the course of this study were obtained with 5 mg of 955 (Z)(E)-11-tetradecen-1-yl acetates containing 0.5–10% (Z)-11-tetradecen-1-ol (approx. 1%Eisomer) in polyethylene caps. No evidence was found for the presence of (Z)-11-tetradecenal in female tip extracts, and this compound was found to be ineffective in increasing trap catches.Lepidoptera: Tortricidae: Tortricinae.This research was supported in part by the Rockefeller Foundation, and by NSF Grant No. GB-38020.     

Calling behavior and pheromone titer in the smaller tea tortrix moth,Adoxophyes sp. (Lepidoptera: Tortricidae)

The calling behavior and pheromone titer in the female smaller tea tortrix moth,Adoxophyes sp., were investigated under a 1410-hr light-dark photoperiod. Quantitative gas chromatographic analysis of ovipositor extract for (Z)-11-tetradecenyl acetate (Z11–14Ac) and (Z)-9-tetradecenyl acetate (Z9–14Ac), the major pheromone components of this species, obtained on the third day postemergence, indicated that extractable amounts of sex pheromone were present throughout the period of observation. Maximal pheromone titer and calling activity was reached at 8 and 10 hr after onset of scotophase, respectively. The ratio ofZ11–14Ac toZ9–14Ac through the 24-hr period varied significantly. The significance of the sex pheromone component ratio variation on the attraction of males was tested in a field experiment. The ratio of males trapped by the most attractive blend versus the least attractive one was 2.16.     

Sex pheromone components of the variegated leafroller moth,Platynota flavedana

Female tip extracts of the variegated leafroller moth,Platynota flavedana (Clemens), were analyzed and found to contain a mixture of (E)-11-tetradecen-1-ol and (Z)-11-tetradecen-1-ol (91), as well as a mixture of (E)-11-tetradecenyl acetate and (Z)-11-tetradecenyl acetate (2-31). Small amounts of tetradecen-1-ol and tetradecyl acetate probably are also present. In the field, a mixture of the two alcohols (8416,EZ ratio) attracted significantly more male moths of this species than any other mixture tested. The data indicate that the acetates are probably not used as pheromone components.Lepidoptera:Tortricidae:Tortricinae.This research was supported in part by the Rockefeller Foundation and by NSF Grant No. GB-38020.     

Identification and field testing of additional components of female sex pheromone of African armyworm,Spodoptera exempta (Lepidoptera: Noctuidae)

Ovipositor washings from virgin femaleSpodoptera exempta (Walker) (Lepidoptera: Noctuidae) were analyzed by high-resolution gas chromatography (GC) linked to a male electroantennogram (EAG). GC retention times of the two major EAG responses observed were consistent with their assignment as (Z)-9-tetradecenyl acetate and (Z,E)-9,12-tetradecadienyl acetate, as previously identified. However, three other EAG responses were also noted that had GC retention times consistent with (Z)-9-tetradecenal, (Z)-9-tetradecen-1-o 1, and (Z)-11-hexadecenyl acetate. The components were present in the ratio of 10051.53.54, respectively. Further analysis of the ovipositor washings by GC linked to a mass spectrometer (GC-MS) confirmed these findings and indicated the presence of a sixth component consistent with (Z)-11-tetradecenyl acetate present at 2 % of the major component. In field tests carried out in Kenya, (Z)-11-hexadecenyl acetate was the only newly identified component to enhance the catch of the original two-component mixture when presented in their natural ratio. The addition of (Z)-9-tetradecen-1-ol reduced catch, while (Z)-9-tetradecenal and (Z)-11-tetradecenyl acetate had no apparent effect.     

Identification of a four-component sex pheromone of the female oriental fruit moth,Grapholitha molesta (Lepidoptera: Tortricidae)

The female-emitted pheromone ofGrapholitha molesta (Busck), the Oriental fruit moth, was collected by holding females in glass flasks during calling. Flask washes were found to contain four pheromone components: (Z)-8-dodecenyl acetate and (E)-8-dodecenyl acetate in a 1007 ratio, and (Z)-8-dodecen-1-ol and dodecanol in a 10020 ratio. The ratio of (Z)-8-acetate to (Z)-8-dodecen-1-ol was approx. 10030. Approximately 0.1–0.2 ng of pheromone was recovered per female per hour of calling.Published as Journal Article No. 8598 of the Michigan State University Agricultural Experiment Station.     

Sex pheromone of the armyworm,Pseudaletia unipuncta (Haworth) (Lepidoptera: Noctuidae)

(Z)-11-Hexadecen-1-ol acetate (Z11–16Ac) free of theE isomer (<1%), hexadecan-1-ol acetate (16 Ac), and a hexadecen-1-ol [the (Z)-11 isomer based on the retention time on a Carbowax capillary column] were identified in extracts of the sex pheromone glands of adult virgin female armyworms,Pseudaletia unipuncta. Also, gas Chromatographic retention times on polar and nonpolar columns indicated the possible presence of (Z)-9-hexadecen-1-ol acetate (Z9–16Ac). The ratioZ11–16Ac/16Ac/Z11–16OH/Z9–16Ac was 10.150.130.02. Infield testsZ11–16 Ac was attractive alone, and the addition ofZ9–16Ac,Zll–16 OH, or 16 Ac singly or in combination in ratios found in the gland did not increase trap capture.Mention of a proprietary product does not constitute an endorsement of this product by the USDA.     

Sex pheromone evidence for two distinct taxa withinGraphania mutans (Walker)

The sex pheromones of two populations ofGraphania mutans (Walker) were analyzed. Females from an Auckland population produced (Z)-9-tetradecenol (Z9-14OH), (Z)-9-tetradecenyl acetate (Z9-14OAc), (Z)-7-tetradecenol (Z7-14OH) and (Z)-7-tetradecenyl acetate (Z7-14OAc), while females from a Lincoln population produced these four compounds and a large amount of (Z)-9-tetradecenal (Z9-14Ald). Significant differences, paralleling the difference between females, were observed when the responses of males of both populations to the above and other related compounds were tested by electroantennogram, field-trapping, and wind-tunnel bioassays. The most distinct difference was observed in the wind tunnel. Males from both taxa flew upwind and touched pheromone sources containing sex pheromone extract of females of their own taxon, but either did not initiate upwind flight or arrested upwind flight shortly after taking flight in response to extract from females of the other taxon. The difference between the pheromone systems of the two populations is probably due to the presence and importance of Z9-14Ald in the pheromone blend of the Lincoln population. Thus the addition of a relatively large amount of Z9-14Aid to a four-component pheromone blend (i.e., Z9-14OH, Z9-14OAc, Z7-14OH, andZ7-14OAc) attractive to Auckland males completely suppressed trap catches of male G.Mutans in Auckland but large numbers of males were caught at both Lincoln and Nelson in traps baited with this five-component blend. In wind-tunnel studies, the addition of even small (1% of amount of Z9-14OH) amounts ofZ9-14Ald to the four-component blend resulted in a significantly greater proportion of Auckland males arresting upwind flight than to the four-com ponent blend. It is suggested that these two populations of G. nations represent distinct sibling species within the described concept.LepidopteraNoctuidaeHadeninae.     

Individual variation in sex pheromone of smaller tea tortrix moth,Adoxophyes sp. (Lepidoptera: Tortricidae)

Female smaller tea tortrix mothsAdoxophyes sp. (Lepidoptera: Tortricidae), which initiated calling at 1, 2, or 3 days old, respectively, were analyzed individually for (Z)-11-tetradecenyl acetate (Z11-14:OAc) and (Z)-9-tetradecenyl acetate (Z9–14: OAc) in the pheromone gland via GLC. Among different age groups, broad and similar distributions were found for pheromone quantity (¯X=58.6±52.9 ng/female; range 1.3–219.8 ng/female). The ratio of the two pheromone components averaged 6535 but ranged from 8416 to 4060. The significance of the pheromone blend variation to the attraction of males was tested in a field experiment. The ratio of males trapped by the most attractive blend versus the least attractive one was 2.2.     

Identification and field testing of female-produced sex pheromone components of the spring cankerworm,Paleacrita vernata Peck (Lepidoptera: Geometridae)

Two sex pheromone components, 3(Z),6(Z),9(Z)-nonadecatriene (3Z,6Z,9Z-19 H), and 3(Z),6(Z),9(Z)-eicosatriene (3Z,6Z,9Z-20 H), have been positively identified, and a third component, 6(Z),9(Z)-nonadecadiene (6(Z),9(Z)-19 H) has been tentatively identified from abdominal tip extracts of female spring cankerworm moths,Paleacrita vernata Peck (Lepidoptera Geometridae). The pheromone components were identified by a combination of gas chromatography, electroantennography, mass spectrometry, chemical tests, comparison with standards, and field testing. Only 3Z,6Z,9Z-20 H exhibited significant attractant activity when tested alone, and it was potentiated by the other two components. The attractive blend was an 821 ratio of 3Z,6Z,9Z-20H/3Z,6Z,9Z-19H/6Z,9Z-19H. However, the two-component blend of 3Z,6Z,9Z-20 H and 6Z,9Z-19 H (81 ratio) was as attractive as the three-component blend in further field tests. A series of related compounds, the diene monoepoxides available from epoxidation of C₁₉ and C₂₀ 3Z,6Z,9Z-trienes, some of which have been found in the pheromone blends of other moth species, were tested as behavioral antagonists. The attraction of male moths to synthetic lures was suppressed by the addition of 6Z,9Z-cis-3,4-epoxy-nonadecadiene to the lures. Additional experiments were performed to determine the effects of lure dosage, trap height, and trap design on the numbers of male moths captured.Issued as NRCC 30711.     

Sex pheromone components of the blueberry leaftier mothCroesia curvalana kearfott (Lepidoptera: Tortricidae)

The GC-MS and GC-EAD analyses of sex-gland components and sex-gland-released volatiles have identified (E)- and (Z)-11-tetradecenal (9010) and (E)- and (Z)-11-tetradecenyl acetate (8515) as components of the sex pheromone chemical communication system ofCroesia curvalana (Kearfott). The aldehyde-to-acetate ratio of 91 was found in the gland-released components. This blend at a 0.1–1 g/day release rate from PVC lures was shown to be as effective as virgin females in the trapping of maleC. curvalana.