Identification and synthesis of insect pheromone

(Z,Z)-3,13-Octadecadien-1-ol1a is identified as the sex pheromone from the poplar pole clearwing moth,Sphecia siningensis Hsu, by GCMS analysis, synthesis, EAG, and field bioassay. Species isolation among Sesiidae by pheromone is also discussed.Studies on the identification and synthesis of insect pheromone XXVII. Stereoselective synthesis of (5R, 6S)-(–)- and (5S, 6R)-(+)-mosquito oviposition attractant pheromone and stereochemistry of asymmetric addition of a chiral sulfoxide to a chiral aldehyde. Zhou, W.S., Cheng, J.F. and Lin, G.Q.,Acta Chemica Sinica 46:274, 1985.     

Structure-activity correlations among analogs of the currant clearwing moth pheromone

Eleven analogs of (E,Z)-2,13-octadecadien-1-yl acetate1, a main pheromone component of the currant clearwing moth,Synanthedon tipuliformis Clerk (Lepidoptera: Sesiidae) were synthesized and tested for their biological activities by electroantennography (EAG). To correct the EAG data for differences in volatility of the analogs, their vapor pressures were estimated by a gas chromatographic method. All structural changes in the parent molecule were found to reduce the biological activity to various degrees. The most active analog tested was the carbamate12, whose activity was almost comparable to that of the pheromone component1. Structure-activity correlations showed that hydrophobic, steric, and electronic effects of chain terminal groups might be responsible for variations in biological activity of the conformationally unchanged (E,Z)-2,13-analogs     

Chemical conversion of 9-tetradecen-1-ol acetates to 3,13-octadecadien-1-ol acetates,sex attractants for male clearwing moths (Lepidoptera: Sesiidae)

Males of many species of clearwing moths are attracted by one of the geometrical isomers of 3,13-octadecadien-1-ol acetate or by a mixture of isomers. The synthesis of (E,Z)-, (E,E)-, and (Z,E)-3,13-octadecadien-1-ol acetate is described starting with the (Z)- and (E)-9-tetraceden-1-ol acetates, which are commercially obtainable.     

Compounds modifying male responsiveness to main female sex pheromone component of the currant borer,Synanthedon tipuliformis clerk (Lepidoptera: Sesiidae) under field conditions

Various blends of (E,Z)-2,13-octadecadien-1-ol acetate (E,Z2,13-18: OAc), (Z)-13-octadecen-1-ol acetate (ZOAc) (two previously identified pheromone components of the currant borer,Synanthedon tipuliformis females), (E,Z)-, (Z,Z)-3,13-octadecadien-1-ol acetates (E,Z- andZ,Z3,13–18:OAc), andZ,Z-3,13-octadecadien-1-ol (Z,Z3,13–18:OH) were evaluated in field traps in three geographic regions. MaleS. tipuliformis were attracted toE,Z2,13–18:OAc in Tasmania, New Zealand, and Hungary. Captures were not influenced by the addition ofZ13–18: OAc, tested in Tasmania and Hungary. In Hungary and New Zealand, the addition ofE,Z3,13–18: OAc toE,Z2,13–18:OAc in a ratio of 100:3 was strongly synergistic; however, in Tasmania captures were reduced. The addition ofZ,Z3,13–18: OAc toE,Z2,13–18:OAc in a ratio of 101 resulted in strong inhibition of trap captures in Hungary. WhenZ,Z3,13–18: OAc was added in different ratios to a 100:3 binary mixture ofE,Z2,13–18:OAc/E,Z3,13–18:OAc in Hungary, it strongly reduced captures at, or above a ratio of 10033 but no decrease was recorded at a ratio of 10031. In New Zealand and Tasmania it reduced captures at a ratio of 10031. Observations of behavioral responses of maleS. tipuliformis in Hungary to synthetic baits in the field showed thatE,Z2,13–18:OAcby itself evoked close-range approaches to the source from only 20% of males, whereas the addition ofE,Z3,13–18:OAc in a ratio of 1003 raised that value to 65 %. Landing on the source was significant only at sources with a 10030.1310 blend ofE,Z2,13–18:OAc/E,Z3,13–18: OAc/Z,Z3,13–18: OAc/Z,Z3,13–18: OH/Z13–18: OAc. A 1003 binary mixture ofE,Z2,13–18:OAc/E,Z3,13–18:OAc in a dose range of 10–1000 g can be recommended for more effective field monitoring ofS. tipuliformis populations in Hungary and in New Zealand. In Tasmania, at present,E,Z2,13–18: OAc by itself is the most potent sex attractant of the species.     

Sex pheromone of fall armyworm,Spodoptera frugiperda (J.E. Smith)

Analyses of extracts of pheromone glands and of volatiles from calling female fall armyworm moths,Spodoptera frugiperda (J.E. Smith), revealed the presence of the following compounds: dodecan-1-ol acetate, (Z)-7-dodecen-1-ol acetate, 11-dodecen-1-ol acetate, (Z)-9-tetradecenal, (Z)-9-tetradecen-1-ol acetate, (Z)-11-hexadecenal, and (Z)-11-hexadecen-1-ol acetate. The volatiles emitted by calling females differed from the gland extract in that the two aldehydes were absent. Field tests were conducted with sticky traps baited with rubber septa formulated to release blends with the same component ratios as those emitted by calling females. These tests demonstrated that both (Z)-7-dodecen-1-ol acetate and (Z)-9-tetradecen-1-ol acetate are required for optimum activity and that this blend is a significantly better lure than either virgin females or 25 mg of (Z)-9-dodecen-1-ol acetate in a polyethylene vial, the previously used standard. Addition of the other three acetates found in the volatiles did not significantly increase the effectiveness of the two-component blend as a bait for Pherocon 1C or International Pheromones moth traps.Mention of a commercial or proprietary product does not constitute an endorsement by the USDA.     

Sex attractant for currant clearwing mothSynanthedon tipuliformis (Clerck) (Lepidoptera: Sesiidae)

The currant clearwing moth,Synanthedon tipuliformis (Clerck) (Lepidoptera: Sesiidae), is a pest in many parts of the world. In field tests it was found that (E,Z)-2,13-octadecadien-1-ol acetate attracts males of this species. The synthesis of this compound and of its geometrical isomer (Z,Z)-2,13-octadecadien-1-ol acetate is described.     

Sex pheromone of fall armyworm

Two components of the fall armyworm,Spodoptera frugiperda (J.E. Smith), sex pheromone, (Z)-9-dodecen-1-ol acetate (DDA) and (Z)-9-tetradecen-1-ol (TDA), were tested alone and in combination to determine their effects on male sexual response and inhibition of mating in the laboratory. The threshold response for FAW males was lower for TDA than for DDA, and males responded to TDA over a wider range of dosages. Although TDA is not attractive to FAW males in the field, this compound was highly effective in reducing mating under laboratory conditions.cooperating with the Insect Attractants, Behavior, and Basic Biology Research Laboratory, Gainesville, Florida 32604.     

Sex pheromone of hickory shuckwormCydia caryana Development of an effective field Lure

Extracts of the sex pheromone glands of femaleCydia caryana were evaluated by electroantennography and gas chromatography-mass spectrometry. These studies suggested the following compounds were potential sex pheromone components: (Z)-8- and/or (E)-9-dodecenyl acetate (50 pg/female), dodecyl acetate (40 pg/female), and (E, E)-8,10-dodecadienyl acetate (25 pg/female). In field tests only the diene produced trap catch, and when the other components were added to the diene, trap catch was not increased. When the diene was formulated in red natural rubber septa, only transient and low catches were obtained, but when gray halobutyl isoprene elastomeric septa were used, high and consistent catches were obtained for eight weeks. Catches depended on the ratio of (E, E)-8,10 to (E, Z)-8,10 isomers. High catches were obtained for anEE toEZ ratio of 100 0.6, and insignificant catches were obtained when the ratio was 100 3. Equivalent catches were obtained for dosages of 50, 100, and 200 g/septum.     

Study of female sex pheromone of leopard moth,Zeuzera pyrina L. Isolation and identification of three components

Three compounds have been identified in the abdominal tip extracts from the female leopard moth,Zeuzera pyrina L. Gas-liquid chromatography and mass spectroscopy data showed that (E, Z)-2, 13-octadecadien-1-ol acetate was the main component and that (Z)-13-octadecen-1-ol acetate and octadecan-1-ol acetate were secondary components. The electroanten-nographic responses of maleZ. pyrina to nanogram amounts of all four 2, 13-octadecadien-1-ol acetate isomers indicated that theE, Z isomer had the maximum activity. A strong EAG response was also recorded for (Z)-7-do-decen-1-ol acetate, which was not detected in the female extracts.     

Sex Pheromone of the Dogwood Borer, <Emphasis Type="Italic">Synanthedon scitula</Emphasis>

The sex pheromone of female dogwood borers (DWB) Synanthedon scitula (Harris) (Lepidoptera: Sesiidae) was determined to be an 88:6:6 ternary blend of (Z,Z)-3,13-octadecadienyl acetate (Z,Z-3,13-ODDA), (E,Z)-2,13-octadecadienyl acetate (E,Z-2,13-ODDA), and (Z,E)-3,13-octadecadienyl acetate (Z,E-3,13-ODDA) by gas chromatography–electroantennographic detection (GC–EAD) and gas chromatography–mass spectrometry (GC–MS). The major sex pheromone component, Z,Z-3,13-ODDA, was attractive as a single component. A blend of Z,Z-3,13-ODDA with 1–3% of E,Z-2,13-ODDA (binary blend) was more attractive than the single component. A third component, Z,E-3,13-ODDA, was sometimes observed in GC–EAD analyses, and enhanced attraction to the binary blend in some field bioassays. Lures containing 1 mg of binary and ternary blends attracted 18 and 28 times more male DWB moths, respectively, than caged virgin females in field trials. Attraction was strongly antagonized by addition of as little as 0.5% of E,Z-3,13-octadecadienyl acetate (E,Z-3,13-ODDA). In a period of 12 wk in 2004, more than 60,000 males were captured in sticky traps baited with synthetic pheromone blends in six apple orchards in Virginia, West Virginia, and North Carolina. Lure longevity trials showed that ∼76% of the pheromone remained in rubber septum lures after 12 wk in the field.     

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 of sex pheromone components of jack pine budworm,Choristoneura pinus pinus freeman

Chemical identification and field-trapping experiments have shown that a blend of 8515 (E,Z)-11-tetradecenyl acetates and 8515 (E,Z)-11-tetradecen-1-ols (in a 91 ratio) are female sex pheromone components for jack pine budworm,Choristoneura pinus pinus. This blend of chemicals, formulated in PVC (0.1 %, w/w) sources is as effective a trap bait as virgin females. Preliminary wind tunnel observations have indicated that this blend, effective as a trap bait, is not equivalent to females.Lepidoptera: Tortricidae.     

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.     

Sex pheromone of European corn borer.

Sex gland extracts ofOstrinia nubilalis females collected in the wild or laboratory-reared from Switzerland, Italy, and Hungary were analyzed. Individuals collected in the north of Switzerland contained (Z)- and (E)-11-tetradecenyl acetate at the approximate ratio of 973 (Z type), in accordance with field responses of males and previous findings. On the other hand, females from a laboratory culture derived from field collections made in the same area and reared for four to five generations contained theZ andE isomers at ratios of ca. 397 and 3565, respectively. In the south, one of the eight wild females analyzed was of theZ type and the rest intermediate, whereas males were predominantly trapped with blends of the two isomers containing 60 to 97E. In a laboratory culture reared for one to two generations from corn borers collected in Hungary, three of nine females were of the intermediate type and the restZ. Small amounts of (Z)-11-hexadecenyl acetate were detected in female glands of theE strain; however, no effect of this compound could be observed in the field.     

C18 Dienes as attractants for eighteen clearwing (Sesiidae), tineid (Tineidae), and choreutid (Choreutidae) moth species

By screening singly and binary mixed 2,13- and 3,13-octadecadien-yl acetates and alcohols (2,13- and 3,13-18: Ac/OH)in Lithuania, Armenia, Azerbaijan, Turkmenistan, Ukraine, and the far east of Russia, sex attractants were discovered for 12 Sesiidae, four Tineidae, and one Choreutidae moth species. Males ofSesia yezoensis andBembecia puella as well asNemapogon flavifrons were attracted by mixture ofZ3,Z13-18:Ac/OH in a ratio of 91,Pyropteron sp. n. by the same mixture (ratio 19),Bembecia romanovi andB. zuwandica byZ3,Z13-18:Ac andE3,Z13-18:Ac (91),Synanthedon caucasicum by the same mixture in the opposite ratio (19),B. scopigera by 23,213-18:Ac andE2,Z13-18:OH in a ratio 91,Synasphecia triannuliformis byZ3,Z13-18:OH andE3,Z13-18:OH (91),Similipepsis takizawai andArchimeessia sp. n. by E3,Z13-18:OH andE2,Z13-18:Ac (11),Prochoreutis sechestediana by a mixture ofE3,Z13-18:Ac plusE2,Z13-18:OH (1),Microsphecia brosiformis by E3,Z13-18:Ac,Synanthedon conopiformis by the analogous alcohol,Synanthedon scoliaeformis andNemaxera betulinella byE2,Z13-18:Ac,Triaxomera fulvimitrella byZ3,Z13-18:Ac. An analogous alcohol component is essential for the attraction ofB. ichneumoniformis males. Inhibitors forB. romanovi, B. scopigera andB. zuwandica attraction were discovered. Preliminary data on attractants for six other species as well as on the diurnal rhythm of sexual activity of three species are presented. A new method for the stereoselective synthesis of 3,13–18:Ac/OH andE2,Z13-18:Ac/OH is described.     

Filbertworm sex pheromone

(E,E)- and (E,Z)-8,10-Dodecadien-1-ol acetates were identified in a 14.3 ratio in the extract of abdominal tips of female filbert-worm moths,Melissopus latiferreanus (Walsingham). The identifications were based on electroantennogram (EAG) analysis, gas chromatography, mass spectrometry, ozonolysis, and synthesis. TheE,Z isomer produced the stronger EAG response. In the field tests of various ratios ofE,EE,Z, the ratio found in the extract captured the most males. The pureE,E isomer initially was not attractive by itself (<0.1%E,Z) but became attractive after a few days, presumably because of isomerization. TheE, Z isomer (<0.1%E,E) was attractive initially, but this compound might have isomerized faster than theE,E isomer. A study of the isomerization showed that regardless of the initial mixture of 8,10-dodecadien-1-ol acetate isomers, almost complete equilibration existed after one month. The equilibrium mixture consisted of 9%Z8,E10, 65%E8,E10, 23%E8,Z10, and 3%Z8,Z10. Concentrations in rubber septa (14 ratio ofE,E toE,Z) of 0.03–3.0 mg/septum produced equivalent trap catches.This paper reports the results of research only. Mention of a commercial product in this paper does not constitute a recommendation by the U.S. Department of Agriculture.     

Sex pheromone components of the fruit-tree leaf roller,Archips argyrospilus (Walker) (Lepidoptera: Tortricidae), in British Columbia

In field experiments in the Okanagan Valley, British Columbia, the pheromone blend of (11Z)-tetradecen-1-ol acetate (Z11-14:OAc), (11E)-tetradecen-1-ol acetate (E 11-14:OAc), (9Z)-tetradecen-1-ol acetate (Z9-14:OAc) and dodecan-1-ol acetate (12: OAc) at a 1006421 ratio (western FTLR blend) attracted significantly more male fruit-tree leaf roller (FTLR),Archips argyrospilus (Walker), than did the previously reported four-component blend and modifications thereof. Addition of (11Z)-tetradecen-1-ol (Z11-14:OH) to the western FTLR blend in a ratio of 4% relative toZ11-14: OAc further significantly enhanced attraction. Compounds were identified and their ratio determined by coupled gas chromatographic-electroantennographic (GC-EAD) and coupled GC-mass spectrometric analyses of female FTLR pheromone gland extracts and by retention index calculations of candidate pheromone components. Determination and use of geographically specific pheromonal blends may be required for optimal, semiochemical-based biorational control of FTLR and other lepidopteran orchard pests.     

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.     

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 and Field Evaluation of Components of Female Sex Pheromone of Millet Stem Borer, Coniesta ignefusalis

Five active compounds were detected during analyses of ovipositor washings and effluvia from virgin female Coniesta ignefusalis moths by gas chromatography (GC) linked to electroantennographic (EAG) recording from a male moth. These were identified as (Z)-7-dodecen-1-ol (Z7–12:OH), (Z)-5-decen-1-ol (Z5–10:OH), (Z)-7-dodecenal (Z7–12:Ald), (Z)-7-dodecenyl acetate (Z7–12:Ac), and (Z)-9-tetradecen-1-ol (Z9–14:OH) by comparison of their GC retention times, mass spectra, and EAG activities with those of synthetic standards. Laboratory tests of dispensers for these compounds showed that release rates from polyethylene vials increased to relatively uniform values after three to four days, but release from septa was very rapid and nonuniform and decreased to low levels after two to three days. Trapping tests in Niger showed that the major component, Z7–12:OH, and two of the minor components, Z5–10:OH and Z7–12:Ald, were essential for attraction of male C. ignefusalis moths. The most attractive blend contained these three components in a 100:5:3.3 ratio in a polyethylene vial, which emitted the components in similar proportions to those produced by the female C. ignefusalis moth. Water traps baited with this blend containing 1 mg of Z7–12:OH caught more male C. ignefusalis moths than traps baited with newly emerged female moths. Addition of up to 10% of the corresponding E isomers of the pheromone components had no effect on catches, but addition of the other two minor components detected, Z7–12:Ac and/or Z9–14:OH, to the attractive blend at naturally occurring levels caused significant reductions in trap catch.