Identification of the sex pheromone of the yellow scale

The sex pheromone of the yellow scale,Aonidiella citrina (Coquillett), was isolated from airborne collections and found to be (E)-3,9-dimethyl-6-isopropyl-5,8-decadien-1-yl acetate. Aonidiella citrina (Coquillett) (Homoptera: Diaspididae).This research was supported by a USDA cooperative research grant.     

Synthesis of 7-methyl-3-methylene-7-octen 1-yl propanoate and (z)-3,7-dimethyl-2, 7-octadien-1-yl propanoate,components of the sex pheromone of the san jose scale

The two components of the sex pheromone of the San Jose scale,Quadraspidiotus perniciosus (Comstock) were synthesized. The first component, 7-methyl-3-methylene-7-octen-1-yl propanoate, was obtained by the addition of a 4-methyl-4-penten-1-yl copper complex to 3-butyn-1-yl propanoate (or 3-butyn-1-yl trimethylsilyl ether). Reaction of the same copper complex with propyne followed by treatment with carbon dioxide gave a key intermediate in the stereoselective synthesis of (Z)-3,7-dimethyl-2,7-octadien-1-yl propanoate, the second component of the pheromone.Quadraspidiotus perniciosus (Comstock) (Homoptera: Diaspididae).Contribution No. 73 from the Research Laboratory of Zoecon Corporation.     

Identification of the California red scale sex pheromone

Pheromone components of female California red scale,Aonidiella aurantii (Maskell) were isolated from airborne collections and found to be 3-methyl-6-isopropenyl-9-decen-1-yl acetate and (Z)-3-methyl-6-isopropenyl-3,9-decadien-1-yl acetate. Both enantiomers of the latter compound as well as the corresponding enantiomers of theE isomer were prepared from (S)- or (R)-carvone. Bioassays with each of the four isomers showed that only theR,Z isomer attracted male red scale. Aonidiella aurantii (Maskell) (Homoptera: Diaspididae).This research was supported by a USDA Cooperative Research Grant.     

Synthesis and identification of a third component of the San Jose scale sex pheromone

Two components of the San Jose scale sex pheromone had previously been identified as 7-methyl-3-methylene-7-octen-1-yl propanoate (I) and (Z)-3,7-dimethyl-2,7-octadien-1-yl propanoate (II). An isomer and various homologs have subsequently been synthesized and tested in a greenhouse bioassay. TheE isomer of II (XI) was found to be attractive to male scales. This compound has now been isolated and identified from airborne extracts of virgin female scales. The composition of the natural pheromone was 48.5%, 46.7%, and 4.8% of I, II, and XI, respectively. In field tests in California and New York, synthetic XI was found to be attractive to male scales alone and in combination with I and II, but there was no obvious increase in trap catch when the synthetic isomers were present in the same ratio as in the natural blend. Quadraspidiotus perniciosm (Comstock) (Homoptera: Diaspididae)     

(Z,Z)-4,7-tridecadien-(S)-2-yl acetate: sex pheromone of Douglas-fir cone gall midge,Contarinia oregonensis

Our objectives were to identify and field test the sex pheromone of female Douglas-fir cone gall midge, Contarinia oregonensis (Diptera: Cecidomyiidae). Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone extract revealed a single compound (A) that elicited responses from male antennae. Hydrogenation of pheromone extract, followed by renewed GC-EAD analysis, revealed a new EAD-active compound with chromatographic characteristics identical to those of tridecan-2-yl acetate on five fused silica columns (DB-5, DB-210, DB-23, SP-1000, and Cyclodex-B). Syntheses, chromatography, and retention index calculations of all possible tridecen-2-yl acetates suggested that the candidate pheromone A was a tridecadien-2-yl acetate with nonconjugated double bonds. Synthetic candidate pheromone component (Z,Z)-4,7-tridecadien-2-yl acetate (Z4Z7) cochromatographed with A on all analytical columns and elicited comparable antennal activity. In GC-EAD analyses that separated the enantiomers (Z,Z)-4,7-tridecadien-(S)-2-yl acetate (2S-Z4Z7) and (Z,Z)-4,7-tridecadien-(R)-2-yl acetate (2R-Z4Z7) with baseline resolution, only 2S-Z4Z7 as a component in a racemic standard or in pheromone extract elicited antennal responses. In Douglas-fir seed orchards, sticky traps baited with 2S-Z4Z7 captured male C. oregonensis, whereas 2R-Z4Z7 was behaviorally benign. Comparable catches of males in traps baited with racemic Z4Z7 (50 g) or virgin female C. oregonensis suggested that synthetic pheromone baits could be developed for monitoring C. oregonensis populations in commercial Douglas-fir seed orchards.     

Attractant lures for males of the pea moth,Cydia nigricana (F.) Containing (E)-10-dodecen-1-yl acetate and (E,E)-8,10-dodecadien-1-yl acetate

Lures containing different amounts of (E)-10-dodecen-1-yl acetate and (E,E)-8, 10-dodecadien-1-yl acetate were formulated in natural rubber stoppers or polyethylene vials and tested in traps in the field to establish relative attractiveness to males of the pea moth,Cydia nigricana (F.), dose-response relationships, and the effects of weathering. Initially, both formulations of (E,E)-8,10-dodecadien-1-yl acetate were much more attractive than those of (E)-10-dodecen-1-yl acetate, but their activity diminished considerably after only 5 days in the field because an inhibitor was formed, and polyethylene formulations were not attractive after one week. However, lures containing (E)-10-dodecen-1-yl acetate, with or without antioxidants, in both rubber and polyethylene were still attractive after three months' exposure in the field and are therefore suitable for practical monitoring of pea moth populations.     

Behavioral response of male white peach scale to the sex pheromone, (R,Z)-3,9,-dimethyl-6-isopropenyl-3,9-decadien-1-ol propionate and corresponding alcohol

Males of the white peach scale,Pseudaulacaspis pentagona (Tar-gioni-Tozzetti), in Florida differ from this scale in France in their responses to putative pheromonal chemicals presented in a laboratory bioassay. Males from Florida were attracted to, and exhibited sexual (coputatory) behaviors at, the locus of evaporation of (R,Z)-3,9-dimethyl-6-isopropenyl-3,9-deca-dien-1-ol propionate (P) (previously identified from effluvia of Florida females). Addition of the corresponding primary alcohol (A) to the propionate did not alter the attraction of Florida males to the synthetic P and did not alter their sexual responses from those exhibited by males exposed to P alone. In contrast, the effluvia from French scales has been reported to contain P and A, and the alcohol has been reported in laboratory studies to be required to release sexual behavior in French males. This suggests that the conspecific status of the scale in Florida and France should be reexamined. Field trap baits with 2.5 g of a 1 1 mixture of P and A captured significantly fewer Florida males than traps baited with 1.25 g of P alone, but traps similarly baited with 0.125 g of each material captured the same number of insects as traps baited with 0.125 g of P alone.Mention of a commerical or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Sex pheromone of the San Jose scale

The sex pheromone of the San Jose scale,Quadraspidiotus perniciosus (Comstock), was isolated from airborne collections on Porapak Q. Two components, present in approximately equal amounts, were identified as (Z)-3,7-dimethyl-2,7-octadien-1-yl propanoate and 3-methylene-7-methyl-7-octen-1-yl propanoate. Greenhouse bioassays and field tests have shown that the compounds are independently attractive to male San Jose scale. These structures are compared with those of other known scale pheromones.     

Identification of the white peach scale sex pheromone

Micro techniques were used to obtain spectroscopic and degradative information from less than 5g of the sex attractant of female white peach scale,Pseudaulascaspis pentagons (Targioni-Tozzetti) isolated from airborne collections. The pheromone was identified as (Z)-3,9-dimethyl-6-isopropenyl-3,9-decadien-1-ol propionate. Both enantiomers of theZ isomer and also the enantiomers of theE isomer were prepared from (R)-or (S)-limonene. Bioassays of material with minimum enantiomeric purity of 95% showed that at extreme dilution only theR,Z isomer attracted male white peach scale; however activity of theS,Z enantiomer could not be completely excluded.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Simple and economic syntheses of some (Z)-7- and (Z)-9-alkenyl acetates,and of (E,Z)-7,9-dodecadien-1-yl acetate,the sex pheromone of the European grapevine moth,using aleuritic acid as a common starting material

Short syntheses of (Z)-7-dodecen-1-yl acetate, (Z)-7-tetradecen-1-yl acetate, (Z)-9-dodecen-1-yl acetate, and (Z)-9-tetradecen-1-yl acetate from 7-hydroxyheptanal and 9-oxononanoic acid precursors obtained by oxidative cleavage of easily available aleuritic acid are reported. The key step in these syntheses is a stereoselective Wittig reaction between aldehyde and alkyl-phosphonium salt. Wittig-Horner type reaction of 7-hydroxyheptanal and diethyl cyanomethylphosphonate gave the ,-unsaturated nitrile derivative which after protection of the hydroxyl group was reduced to the corresponding aldehyde. Wittig reaction of the latter, followed by acetylation, completed the synthesis of (E,Z)-7,9-dodecadien-1-yl acetate, the sex pheromone of the European grapevine mothLobesia botrana Schiff.     

Synthesis of the sex pheromone of the Japanese beetle

The stereospecific synthesis of the sex pheromone produced by the female Japanese beetle (Popillia japonica Newman), (R,Z)-5-1-decenyl)-dihydro-2(3H)-furanone, is described. The pure syntheticR,Z form is a powerful attractant for males of the species in field bioassays and was competitive in attractiveness with live females, whereas the racemicZ isomer and theS,Z enantiomer were strong inhibitors of male response. The saturated analogs of both enantiomers were also synthesized stereospecifically.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

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.     

(Z)-9-tetradecen-1-ol acetate

(Z)-9-Tetradecen-1-ol acetate [(Z)-9-TDA], identified originally as the sex pheromone of the fall armyworm,Spodoptera frugiperda (J.E. Smith), acted as a secondary sex pheromone when it was tested in sticky traps in field tests. Low-level synergism was obtained when 2 and 10% quantities of (Z)-9-TDA were added to 100 g of (Z)-9-dodecen-1-ol acetate, which is now considered the primary sex pheromone.Lepidoptera: Noctuidae.In cooperation with the University of Georgia College of Agriculture Experiment Stations, Coastal Plain Station, Tifton, Georgia 31794.Mention of a proprietary product does not constitute endorsement by the USDA.     

Identification of volatile sex pheromone components released by the southern armyworm,Spodoptera eridania (Cramer)

Analysis of sex pheromone gland extracts and volatile pheromone components collected from the calling female southern armyworm,Spodoptera eridania (Cramer), by high-resolution capillary gas chromatography and mass spectroscopy indicated that a number of 14-carbon mono- and diunsaturated acetates and a monounsaturated 16-carbon acetate were produced. Gland extracts also indicated the presence of (Z)-9-tetradecen-1-ol. However, this compound was not found in collections of volatiles. Field trapping studies indicated that the volatile blend composed of (Z)-9-tetradecen-1-ol acetate (60%), (Z)-9-(E)-12-tetradecadien-1-ol acetate (17%), (Z)-9-(Z)-12-tetradecadien-1-ol acetate (15%), (Z)-9-(E)-11-tetradecadien-1-ol acetate (5%), and (Z)-11-hexadecen-1-ol acetate (3 %) was an effective trap bait for males of this species. The addition of (Z)-9-tetradecen-1-ol to the acetate blends tested resulted in the capture of beet armyworm,S. exigua (Hubner), males which provides further evidence that the alcohol is a pheromone component of this species.     

Analysis of field-weathered lures containing (E)-10-dodecen-1-yl acetate,a sex attractant for the pea moth,Cydia nigricana (F.)

Natural rubber stoppers treated with 1, 3, or 10 mg of (E)-10-dodecen-1-yl acetate, an attractant for male pea moth,Cydia nigricana (F.), were exposed in the field during the summer of 1978 and samples analyzed at intervals. The results for all three doses fitted well to first-order loss curves with half-lives of 63.5, 64.7, and 67.3 days, respectively. Thus, lures with an initial dose of 3 mg of the attractant retained approximately 1 mg after 3 months of field exposure; they should therefore maintain a constant level of attractiveness throughout this period because previous field studies showed that moths were equally responsive to fresh lures containing between 1 and 10 mg of the attractant. There was no loss of attractant during the preparation of lures or after 4 months at –15 ° C and only 13% was lost during 3 months of storage at room temperature.     

Mint root borer,Fumibotys fumalis (Guenee): Identification and field tests of female sex pheromone gland components

Compounds identified in sex pheromone gland extracts of femaleFumibotys fumalis (Guenee) consisted of (E,E)-10,12-tetradecadienyi acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, and (Z)-9-tetradecenyl acetate in a ratio of 100:18: 8:4, respectively. The compounds were identified by electroantennographic, gas Chromatographic, mass spectrometric, and chemical derivatization procedures. In mint fields synthetic components in gray elastomeric septa at ratios found in the sex pheromone gland and at doses of 3 or 10 mg of the diene produced trap catch comparable to traps baited with three females.Lepidoptera: Pyralidae     

Female sex pheromone of the Yunnan pine caterpillar moth Dendrolimus houi: first (E,Z)-isomers in pheromone components of Dendrolimus spp

The Yunnan pine caterpillar Dendrolimus houi Lajonquière is a serious defoliator of coniferous forests in southwestern China. Gas chromatography–electroantennography (GC–EAG) analyses of extracts of female sex pheromone glands of D. houi moths revealed the presence of three compounds eliciting antennal responses. These were identified as (5E,7Z)-5,7-dodecadien-1-ol (E5,Z7-12:OH), (5E,7Z)-5,7-dodecadien-1-yl acetate (E5,Z7-12:OAc), and (5E,7Z)-5,7-dodecadienal (E5,Z7-12:Ald) by comparison of their GC retention indices, mass spectra, and EAG activities with those of synthetic standards. Average amounts of E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald per calling virgin D. houi female were 14.7 ± 12.9 ng (± SD), 5.8 ± 5.4 ng, and 0.8 ± 1.4 ng, respectively, in a ratio of 100:39.7:5.6. These three components were also collected from the headspace of calling virgin female moths by solid-phase microextraction (SPME). In addition, trace quantities of (Z)-5-dodecen-1-ol (Z5-12:OH), (5Z,7E)-5,7-dodecadien-1-ol (Z5,E7-12:OH), (5E,7E)-5,7-dodecadien-1-ol (E5,E7-12:OH), (5Z,7E)-5,7-dodecadien-1-yl acetate (Z5,E7-12:OAc), (5Z,7Z)-5,7-dodecadien-1-yl acetate (Z5,Z7-12:OAc), and (5E,7E)-5,7-dodecadien-1-yl acetate (E5,E7-12:OAc) were tentatively identified in female pheromone gland extracts by selected ion monitoring GC-MS. Field trapping experiments showed that E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald were essential for attraction of male D. houi moths. Traps baited with a 20:1:1 blend (alcohol/acetate/aldehyde) loaded on gray rubber septa were as effective as traps baited with virgin female moths. The optimum ratio of acetate to aldehyde was 1:1, and this ratio was more critical than the ratio of either compound to the alcohol. This represents the first example of (E,Z)-isomers in pheromone blends of Dendrolimus species.     

Intrapopulational changes in sex pheromone composition during scotophase in oriental tobacco budworm,Helicoverpa assulta (Guenée) (Lepidoptera: Noctuidae)

Solvent extracts of individual pheromone glands were prepared from femaleHelicoverpa assulta (Guenée) at 2-hr intervals throughout the scotophase. The amounts of female sex pheromone components, (Z)-9-hexadecenal, (Z)-11-hexadecenal, (Z)-9-hexadecenyl acetate, and (Z)-11-hexadecenyl acetate, in the extracts were determined by gas chromatographic analysis. Although females called from early scotophase (2 hr) until late scotophase (6 hr) the quantity of extracted pheromone remained high at 8 hr, the end of the scotophase. More than 70% of the pheromone gland extracts contained sex pheromone components regardless of whether the donor females had been called or resting. Pheromone components were absent from gland extracts prepared at the onset of the scotophase. The quantity of (Z)-9-hexadecenal and (Z)-11-hexadecenal increased rapidly to reach a maximum of approximately 260 and 30 ng/female, respectively, that was maintained for up to 8 hr, the duration of the scotophase. The quantity of (Z)-9-hexadecenyl acetate and (Z)-11-hexadecenyl acetate increased continuously during the scotophase to peak at 600 and 30 ng/female, respectively, 8 hr into the scotophase. At the end of scotophase the quantity of all pheromone components decreased significantly.     

(Z,Z)-7,9-Dodecadienyl acetate,sex pheromone ofEpinotia tedella clerck (Lepidoptera: Tortricidae)

(Z,Z)-7,9-dodecadienyl acetate, a reported male attractant for several New World spp. ofEpinotia, was identified as the primary pheromone of femaleE. tedella (European spruce budmoth) through chemical analysis of pheromone gland washes, the electrophysiological study of male antennal receptor types, and field-trapping tests. The washes contained this compound at a level of approximately 0.4 ng per FE, along with a similar amount of the corresponding alcohol, (Z,Z)-7,9-dodecadien-1-ol. Each compound activated its own specialized type of male receptor cell. No traces of stereoisomers or monoenes were found in the washes. In field-trapping tests conducted in stands of Norway spruce in southern Germany, (Z,Z)-7,9-do-decadienyl acetate as a single chemical proved highly attractive to maleE. tedella over a range of lure doses. The corresponding alcohol or aldehyde did not show attractivity; rather, in binary combinations with the primary pheromone, these compounds, and also the (E,Z)-7,9 stereoisomeric acetate, reduced captures. A 101 blend of (E)-9- and (Z)-9-dodecenyl acetates, reported as anE. tedella male attractant, did not reveal significant captures. No otherEpinotia spp. besidesE. tedella responded to the various 7,9-do-decadienyl test baits during this study.     

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.