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.     

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 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.     

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.     

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.     

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.     

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.     

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 sex pheromone components from pheromone gland volatiles of the tomato looper,Plusia chalcites (Esp.)

The sex pheromone glands ofPlusia chalcites release, dodecyl acetate, (Z)-7-dodecenyl acetate, (Z)-9-dodecenyl acetate, 11-dodecenyl acetate, (Z)-8-tridecenyl acetate, and (Z)-9-tetradecenyl acetate. A combination of capillary GC, GC-MS, and dimethyl disulfide derivatization enabled a rigorous identification of all these compounds, some of which were previously found in gland extracts. Bioassays in a flight tunnel showed that a ternary blend of (Z)-7-dodecenyl acetate, (Z)-9-dodecenyl acetate, and (Z)-9-tetradecenyl acetate elicited directed flights from 85 to 100% of the males tested and elicited copulation attempts, at the end of the flights, from 44 to 74% of the males tested. This blend was equal in activity to the natural gland extract. Addition of the other acetates had only a slight influence on the activity of this mixture. Substitution of either (Z)-9-dodecenyl acetate or (Z)-9-tetradecenyl acetate in this blend by 11-dodecenyl acetate gave two ternary mixtures which also elicited high levels of courtship activity, almost as high as that of the original blend. Addition of (Z)-7-dodecenyl alcohol inhibited almost totally the flight activity of males.Lepidoptera: Noctuidae.Contribution from the Agricultural Research Organization (ARO) No. 1701-E, 1986 series.     

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.     

(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.     

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.     

Sugar beet crown borer,Hulstia undulatella (Clemens) 1: Identification and field tests of female sex pheromone gland components

Electroantennogram profiles of saturated and monounsaturated 12-, 14-, and 16-carbon acetates, and 12- and 14-carbon alcohols implicated (Z)-9-tetradecen-1-ol acetate (Z9-14: Ac) as a component of the female sex pheromone ofHulstia undulatella (Clemens). Gas chromatography-mass spectrometric analysis of extract of the female sex pheromone glands showed the presence of Z9-14:Ac (8.5 ng/female), (Z)-9-tetradecen-1-ol (Z9-14:OH), and (Z)-11-hexadecen-1-ol acetate (Z11-16:Ac) in a ratio of 100421, respectively. In tests in sugar beet fields, Z9-14:Ac alone produced some trap catch. Addition of Z9-14: OH did not increase catch while addition of Z11-16:Ac eliminated catch, but addition of both Z9-14:OH and Z11-16: Ac increased catch sevenfold. A combination of Z9-14: OH and Z11-16: Ac without Z9-14: Ac did not produce trap catch. A lure of 200 g Z9-14:Ac+16 g Z9-14:OH+42 g Z11-16:Ac is suggested for use in monitoring traps.Lepidoptera: Pyralidae: Phycitinae.     

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     

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.