Structure,chirality, and field testing of a male-produced aggregation pheromone of Asian palm weevilRhynchophorus bilineatus (Montr.) (Coleoptera: Curculionidae)

4-Methyl-5-nonanol is a male-produced aggregation pheromone of the Asian palm weevil,Rhynchophorus bilineatus (Montr.). The pheromone was identified by coupled gas chromatographic-electroantennographic detection (GC-EAD) and coupled GC-mass spectrometric (MS) analyses of male-and female-produced volatiles. Analyses by GC-EAD and GC-MS of weevil-produced and stereoselectively synthesized isomers of 4-methyl-5-nonanol on a Cyclodex B column, which separated isomers with baseline resolution, revealed that only (4S,5S)-4-methyl-5-nonanol is EAD active and produced by the males. In field experiments in Papua New Guinea, (4S,5S)-4-methyl-5-nonanol and a racemic mixture of disatereoisomers of it enhanced attraction of male and female weevils to sugarcane-baited traps. (4S,5S)-4-Methyl-5-nonanol is also an aggregation pheromone of two other Asian palm weevils.R. ferrugineus (Oliv.) andR. vulneratus (Panz.). The stereoisomeric mixture of 4-methyl-5-nonanol is currently used to manage populations ofR. bilineatus in Papua New Guinea.     

Aggregation pheromone of palmetto weevil,Rhynchophorus cruentatus (F.) (Coleoptera: Curculionidae)

5-Methyl-4-octanol is the major aggregation pheromone of the palmetto weevil,Rhynchophorus cruentatus (F.). The pheromone (cruentol) was identified by coupled gas chromatographic-electroantennographic (GC-EAD) analysis of male-produced volatiles, coupled GC-mass spectrometry (MS) in electron impact and chemical ionization mode, and coupled GC-high resolution MS. In laboratory and field assays, a diastereomeric mixture of synthetic cruentol greatly enhanced attraction of weevils to cabbage palmetto,Sabal palmetto (Walter), stem tissue, indicating that cruentol and host volatiles are synergistically attractive. An attractive lure in combination with efficient traps should facilitate development of semiochemical-based management forR. cruentatus.     

Laboratory and field evidence for maleproduced aggregation pheromone inRhynchophorus cruentatus (F.) (Coleoptera: Curculionidae)

Laboratory and field assays were conducted to determine if palmetto weevil,Rhynchophorus cruentatus (F.), adults produce an aggregation pheromone. Attraction of females in a Y-tube olfactometer to conspecific males was greater than to clean air. Male and female attraction to conspecific male volatiles combined with host-palm,Sabal palmetto (Walter), volatiles was greater than to host-palm volatiles alone. Similarly, more weevils were caught in the field in traps baited with conspecific males plus host-palm tissue than in similar traps baited with only males, or palm tissue, or females, or females plus palm tissue. These results suggest thatR. cruentatus males produce an aggregation pheromone(s) that is highly attractive to conspecific adults of both sexes when combined with host-palm volatiles. This study is an important step towards understanding the chemical ecology ofR. cruentatus.     

Pheromone chirality of asian palm weevils,Rhynchophorus ferrugineus (Oliv.) andR. vulneratus (Panz.) (Coleoptera: Curculionidae)

Production of 4-methyl-5-nonanol, and 4-methyl-5-nonanone by two sympatric Asian palm weevils,Rhynchophorus ferrugineus (Oliv.) andR. vulneratus (Panz.) suggested that enantiospecificity of either compound could impart species specificity of pheromone communication. Weevil-produced, racemic 4-methyl-5-nonanol and 4-methyl-5-nonanone and their stereoselectively synthesized optical isomers were subjected to gas chromatographic-electroantennographic detection (GC-EAD) and GC-mass spectrometry (MS) on a chiral Cyclodex-B column. Only theS,S stereoisomer of 4-methyl-5-nonanol was EAD active and was produced by bothR. ferrugineus andR. vulneratus. Production and EAD activity of (S)-4-methyl-5-nonanone exceeded that of its antipode in both weevils. In field experiments in Java. (4S, 5S)-4-methyl-5-nonanol and the stereoisomeric mixture were equally attractive. The 4R,5R stereoisomer was inactive. The corresponding ketone enantiomers neither enhanced nor reduced attraction to (4S,5S)-4-methyl-5-nonanol. Lack of apparent differences betweenR. ferrugineus andR. vulneratus pheromones suggests that synonomy of both weevils should be considered unless other pre- or postzygotic reproductive isolating mechanisms are disclosed in future studies.     

Male-produced aggregation pheromone of the american palm weevil,Rhynchophorus palmarum (L.) (Coleoptera,Curculionidae): Collection,identification, electrophysiogical activity,and laboratory bioassay

Male American palm weevils (APWs),Rhynchophorus palmarum (L.) produced two sex-specific compounds, which were disclosed by volatile collections on Supelpak-2 and gas chromatography. One was a minor compound, not always detected. The major male-produced volatile was identified as (2E)-6-methyl-2-hepten-4-ol through coupled gas chromatography-mass spectrometry and gas chromatography-Fourier transform infrared spectrometry, proton nuclear magnetic resonance spectrometry, and rational synthesis. We propose the trivial name rhynchophorol for this new molecule, which proved to be the essential component of the APW aggregation pheromone by electroantennography, coupled gas chromatography-electroantennography and behavioral bioassays.Research supported in part by the IRHO-CIRAD, Avenue du Val de Montferrand, 34032 Montpellier CEDEX, France.     

Optical isomers of 3,13-dimethylheptadecane: Sex pheromone components of the western false hemlock looper,Nepytia freemani (Lepidoptera: Geometridae)

(3S, 13R)-3, 13-Dimethylheptadecane [(3S, 13R)-3, 13-dime-17Hy] is the major pheromone component of the western false hemlock looper (WFHL),Nepytia freemani. In comparative gas chromotographic-electroantennographic detection (GC-EAD) analyses of stereoselectively synthesized isomers, 1 pg of (3S, 13R)-dime-17Hy elicited significantly stronger electrophysiological responses by male WFHL antennae than did 1 pg of separately injected (3R, 13R)-, (3R, 13S)- or (3S, 13S)-3, 13-dime-17Hy. In field experiments with individually tested stereoisomers. (3S, 13R)-3, 13-dime-17Hy was the only stereoisomer to attract males, but the four-stereoisomer blend was 3.6 times more attractive. Quaternary and all binary combinations of (3S, 13R)-3, 13-dime-17Hy with the other stereoisomers were equally attractive, suggesting that synergisytic behavioral activity in WFHL resided with either one of (3R, 13R)-, (3R, 13S)-, or (3S, 13S)-3, 13-dime-17Hy. Because optical isomers of (di)methylhydrocarbons do not separate on currently available columns, it remains unknown whether female WFHL also produce a four-stereoisomer pheromone blend. Substitutionality of pheromone stereoisomers without loss of behavioural activity has not previously been reported, but favorably compares with the concept of pheromone redundancy that was first suggested for the multiple pheromone component blend of the cabbage looper moth,Trichoplusia ni.     

(R *,S *)-5-hydroxy-4-methyl-3-heptanone male-produced aggregation pheromone ofSitophilus oryzae (L.) andS. zeamais motsch

A male-produced aggregation pheromone, common to the rice weevil,Sitophilus oryzae, and the maize weevil,S. zeamais, was isolated and identified from hexane extracts of highly absorbent paper disks exposed individually to young virgin male weevils. A combination of preparative column and gas-liquid chromatography of disk extracts yielded purified natural pheromone. When analyzed by nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry, the structure of the natural pheromone, sitophilure, proved to be (R ^*,S ^*)-5-hydroxy-4-methyl-3-heptanone, of unknown enantiomeric composition. Synthetic racemic pheromone was highly attractive to males and females of both rice and maize weevils. In addition, both sexes of the granary weevil,S. granarius (L.) were attracted to the racemic preparation.     

Determination of chirality in 5-hydroxy-4-methyl-3-heptanone,the aggregation pheromone ofSitophilus oryzae (L.) andS. zeamais Motschulsky

The chirality of the pheromone of the rice weevil,Sitophilus oryzae (L.), and the maize weevil,S. zeamais (Motschulsky), 5-hydroxy-4-methyl-3-heptanone, was determined using an acetyl lactate derivatization procedure. Maize weevils were shown to produce >98% 4S,5R. Determination was more difficult with rice weevils due to a smaller quantity of insect extract, but they were shown to produce at least 92% 4S, 5R.The attractancy of the four synthetic stereoisomers of 5-hydroxy-4-methyl-3-heptanone was tested using rice and maize weevils. As expected, both species were most strongly attracted to the 4S, 5R enantiomer. Maize weevils also showed low but significant responses (P < 0.05) to both 4R, 5R and 4S,5S. Rice weevils showed a highly significant (P < 0.01) response to 4R, 5S, although it was only about one third the response to 4S, 5R. Thus, (4S,5R)-5-hydroxy-4-methyl-3-heptanone is clearly the major component of the pheromone of bothS. zeamais andS. oryzae.This article reports the results of research only. Mention of a proprietary product does not constitute an endorsement or a recommendation for its use by USDA.     

Evidence for male-produced aggregation pheromone in American palm weevil,Rhynchophorus palmarum (L.) (Coleoptera: Curculionidae):

Field trapping of the American palm weevil (APW),Rhynchophorus palmarum, showed that the combination of caged male APWs and palm stem was much more attractive to APWs of both sexes than palm stem alone. Caged female APWs did not enhance the attractiveness of the palm. Caged APWs without palm stem were not attractive. Virgin laboratory-bred males were highly attractive to APWs of both sexes in a two-choice pitfall olfactometer, whereas virgin laboratory-bred females were not. Adsorbenttrapped volatiles from virgin laboratory-bred males reproduced the effect of living males, giving evidence for a male-produced aggregation pheromone in this species. Wild-mated APWs of both sexes were as responsive to the aggregation pheromone as virgin laboratory-bred APWs. This is the first record of chemical communication in this species. These results have prompted investigations into the chemical identification of the aggregation pheromone.     

Ethyl propionate: Synergistic kairomone for african palm weevil,Rhynchophorus phoenicis L. (Coleoptera: Curculionidae)

Small trunk pieces of a freshly felled 10-year-old oil palm,Elaeis quineensis (Jacq.), were placed in a modified Nalgene desiccator, and volatiles captured for six days on Porapak Q. Gas chromatographic (GC) analysis of Porapak-Q-trapped volatiles with both flame ionization (FID) and electroantennographic detection (EAD) using male or femaleR. phoenicis antennae revealed several EAD-active compounds. They were identified as: ethyl acetate, ethyl propionate, isobutyl propionate, ethyl butyrate, and ethyl isobutyrate. In field experiments in the La Me Research Station, Côte d'Ivoire, ethyl propionate (50 mg/24 hr) but not all esters combined (50 mg/24 hr each) significantly increased capture ofR. phoenicis in pheromone-baited (3 mg/24 hr) traps. One kilogram of 1- to 3-day-old palm tissue was significantly more effective than ethyl propionate in enhancing pheromone attraction. Superior attraction of palm tissue may be attributed to additional as yet unknown semiochemicals. Alternatively, release rates and/or ratios of synthetic volatiles differed from those of palm tissue at peak attraction.     

Chirality of synergistic sex pheromone components of the western hemlock looperLambdina fiscellaria lugubrosa (HULST) (Lepidoptera: Geometridae)

Bakers' yeast reduction of (2E)-3-(2-furanyl)-2-methyl-2-propenal yielded the synthetic intermediate, (2S)-3-(2-furanyl)-2-methylpropanol, of high chiral purity (>97% ee) for the synthesis of the enantiomers of 2,5-dimethylheptadecane and 7-methylheptadecane, two synergistic sex pheromone components of the western hemlock looper (WHL),Lambdina fiscellaria lugubrosa Hulst. In electrophysiological bioassays, (7S)- but not (7R)-7-methylheptadecane elicited strong antennal responses by male WHL antennae. In field trapping experiments, addition of (7S)- but not (7R)-7-methylheptadecane to (5R,11S)-5,11-dimethylheptadecane, the major sex pheromone component of WHL, increased attraction. Attraction to (5R,11S)-5,11-dimethylheptadecane in combination with (7S)-7-methyiheptadecane was further enhanced by the addition of (5S)- but not (5R)-2,5-dimethylheptadecane. Similarly, attraction to (5R,11S)-5,11-dimethylheptadecane combined with (5S)-2,5-dimethylheptadecane increased when 7S- but not (7R)-7-methylheptadecane was added as a third component. We conclude that (7S)-7-methylheptadecane and (5S)-2,5-dimethylheptadecane are the synergistic sex pheromone components of WHL. The synthetic methodology described is applicable to the synthesis of chiral methyl-branched pheromones in other orders of the Insecta, particularly Coleoptera, Diptera and Orthoptera.     

Chirality of 5,11-dimethylheptadecane,the major sex pheromone component of the hemlock looper,Lambdina fiscellaria (Lepidoptera: Geometridae)

Of the four possible stereoisomers of 5,11-dimethylheptadecane, the major sex pheromone component of the eastern hemlock looper (EHL),Lambdina fiscellaria fiscellaria Guen., and the western hemlock looper (WHL),Lambdina fiscellaria lugubrosa Hulst, (5R,11S)-5,11-dimethylheptadecane was the only stereoisomer eliciting electrophysiological responses by male EHL and WHL antennae. In field bioassays with EHL and WHL populations, traps baited with (5R,11S)-5, 11-dimethylheptadecane caught as many males as did traps baited with all four stereoisomers combined or a synthetic mixture of 5,11-dimethylheptadecanes. Catches in traps baited with the other three stereoisomers did not significantly differ from those in the unbaited control traps. We conclude that male antennae lack chemoreceptors for the other three stereoisomers of 5,11-dimethylheptadecane and hypothesize that only (5R,115)-5,11-dimethylheptadecane is produced by female EHLs and WHLs.     

Replacement of carcinogenic alkylating agent ethylene oxide in the synthesis of (Z)-3-dodecen-1-YL (E)-2-butenoate,sex pheromone of sweet-potato weevil,Cylas formicarius elegantulus (summers) andCylas formicarius formicarius (F.)

An alternative synthesis of (Z)-3-dodecen-1-y1 (E)-2-butenoate without use of carcinogenic ethylene oxide and HMPA is described. By coupling of the tetrahydropyranyl (THP) ether of 3-butyn-1-ol with 1-bromooctane with sodamide in liquid ammonia, 12-(2-tetrahydropyranyloxy)-9-dodecyne was obtained; subsequent hydrolysis and semihydrogenation afforded (Z)-3-dodecen-1-ol. The alcohol was then reacted with crotonyl chloride to give the desired crotonate with a total yield of 29.8%. Males of sweet-potato weevil,Cylas formicarius were strongly attracted to the synthetic sex pheromone. The attraction from the dispenser of polyethylene tube was better than the attraction from the dispenser of rubber septum in the field.     

Identification of a novel moth sex pheromone inEriocrania cicatricella (Zett.) (Lepidoptera: Eriocraniidae) and its phylogenetic implications

Extracts from different body parts of adult femaleEriocrania cicatricella (Zett.) were tested for electrophysiological activity on conspecific male antennae. Extracts from the Vth abdominal segment, containing a pair of exocrine glands, elicited the largest electroantennographic response when compared to extracts of other body parts. Female extracts were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). The EAD active peaks were identified as (Z)-4-hepten-2-one, (2R)-heptane-2-ol, and (2R)-(Z)-4-hepten-2-ol by coinjection on a gas chromatography and by comparison of mass spectra with those of synthetic standards. In field tests, a blend of these three pheromone components was highly attractive to conspecific males, and a subtractive assay confirmed that the unsaturated alcohol is the major pheromone component, whereas no definite behavioral activity could be assigned to the ketone or the saturated alcohol. A bait containing the two alcohols withS-configuration was attractive to maleE. sparrmannella (Bosc), whereas no males ofE. cicatricella were found in these traps. The sex pheromone compounds inE. cicatricella are chemically similar to pheromones reported in Trichoptera and they are produced in homologous glands.     

Chemical ecology of the palm weevilRhynchophorus palmarum (L.) (Coleoptera: Curculionidae): Attraction to host plants and to a male-produced aggregation pheromone

Attraction to host plants by adultRhynchophorus palmarum (L.) palm weevils was studied in the field and in the laboratory. Chemical analysis revealed the presence of ethanol and ethyl-acetate in stems of coco palms and in pineapple fruits and of pentane, hexanal, and isopentanol in coco stems. In the olfactometer, the first two compounds and isoamyl-acetate were attractive to the insects and the last three compounds, although not attractive by themselves, increased attractiveness when mixed with the first two compounds. Mixtures of these compounds, in proportions similar to the one occurring in attractive plant tissue, were as attractive as natural coconut tissue. In the field, the chemical compounds, either presented alone or as a mixture, did not attract the weevil. Males produce an aggregation pheromone when smelling ethyl-acetate. Rhynchophorol, 2(E)-6-methyl-2-hepten-4-ol, the known active component of the aggregation pheromone, attracts weevils in the olfactometer and in the field only if plant tissue, ethyl-acetate, or the above-mentioned odor mix are present. We propose that a complex mix of ethanol, ethyl-acetate, pentane, hexanal, isolamyl-acetate, and/or isopentanol serve as a short-range orientation cue to fresh wounds on the plant and that additional host odors, attracting weevils from a distance, have still to be discovered. Rhynchophorol can be considered to be a Synergist, having an anemotactic action at a distance. We recommend the use of retention traps baited with rhynchophorol, ethyl-acetate, and sugar cane as an alternative control method for the pest.     

Isolation and identification of sex pheromone ofSymmetrischema tangolias (Gyen) (Lepidoptera: Gelechiidae)

The sex pheromone of the South American potato tuber mothSymmetrischema tangolias (syn.:Symmetrischema plaesiosema) was identified as a 2:1 mixture of (E,Z)-3,7-tetradecadien-1-ol acetate and (E)-3-tetradecen-1-ol acetate by means of dual-column GC, EAG, GC-EAD, GC-MS, NMR, and wind-tunnel bioassays. (Z)-5-Tetradecen-1-ol acetate and (Z)-7-tetradecen-1-ol acetate were also identified in the pheromone gland extract. MaleS. tangolias were able to detect these acetates (EAG), but their addition to the two-component sex pheromone did not improve attractiveness. Field trials in Cajamarca and Cusco, Peru, showed that traps baited with the synthetic sex pheromone were able to catch large numbers of maleS. tangolias.     

Chirality of israeli pine bast scale,Matsucoccus josephi (homoptera: Matsucoccidae) sex pheromone

The absolute configuration of the sex pheromone of the Israeli pine bast scale,Matsucoccus josephi, was determined as (2E,5R,6E,8E)-5,7-dimethyl-2,6,8-decatrien-4-one, designated here asR-E with 10% (2E,5S,6E,8E)-5,7-dimethyl-2,6,8-decatrien-4-one, designated asS-E. The chirality of the quantitatively minorZ isomer was (2E,5R,6Z,8E)-5,7-dimethyl-2,6,8-decatrien-4-one (R-Z). Chiral assignments were made by comparative gas chromatographic (GC) analysis of naturalM. josephi pheromone with stereoselectively synthesized stereoisomers on a chiral Cyclodex-B column, which separated the enantiomers with baseline resolution. In gas chromatographic-electroantennographic detection (GC-EAD) analysis of the racemicZ andE isomers, the latter elicited the stronger antennal response by maleM. josephi. In GC-EAD of all four stereoisomers, employing the chiral column,R-E was the most active stereoisomer. In field testsR-E attracted 10 times more males ofM. josephi than didS-E. The racemicE/Z pheromone mixture, containing all four stereoisomers in approximately equal amounts, attracted as many maleM. josephi as did an equivalent amount ofR-E, indicating that the other stereoisomers are not inhibitory. The same keto-diene moiety with the same chiral center and configuration in all three known Matsucoccidae sex pheromones implies a common biosynthetic pathway and phylogenetic relationship.Contribution from the Agricultural Research Organization, the Volcani Center, No. 1496-E, 1994 series.Part of the work was performed during a sabbatical leave of E.D. at Simon Fraser University.     

A chiral sex pheromone system in the pea midge, Contarinia pisi

The sex pheromone of the pea midge consists of 2-acetoxytridecane, (2S,11S)-diacetoxytridecane and (2S,12S)-diacetoxytridecane. The responses of male pea midges to the corresponding stereoisomers of (2S,11S)-diacetoxytridecane and (2S,12S)-diacetoxytridecane were tested in field trapping experiments and by electroantennographic recordings. When added at 20% of the pheromone component to the sex pheromone blend, the (2S,11R)- and (2R,11S)-stereoisomers of (2S,11S)-diacetoxytridecane, were shown to have a strong inhibitory effect on male attraction in the field. At the same dose, (2R,11R)-diacetoxytridecane, (2R,12R)-diacetoxytridecane, and meso-2,12-diacetoxytridecane, did not have a significant effect on male behavior. It was also shown that substitution of either (2S,11S)-diacetoxytridecane or (2S,12S)-diacetoxytridecane with the related stereoisomers reduced trap catches to the level of blank traps. The electroantennographic recordings showed similar dose–response curves for the pheromone components and the stereoisomers shown to have an inhibitory effect. It seems likely that male antennae have receptors for both pheromone components and for inhibitory stereoisomers. Scanning electron microscopy and transmission electron microscopy of the antennae revealed three types of sensilla involved in chemoreception: sensilla circumfila, sensilla trichodea, and sensilla coeloconica. The sensilla circumfila and trichodea are both innervated by two sensory cells, whereas the sensilla coeloconica are innervated by four to five cells.     

Aggregation pheromone of square-necked grain beetle,Cathartus quadricollis (Guér.)

When feeding on rolled oats, male square-necked grain beetles,Cathartus quadricollis (Guér.), produced the aggregation pheromone (3R,6E)-7-methyl-6-nonen-3-yl acetate, for which the trival name quadrilure is proposed. The pheromone was highly attractive to both sexes in a two-choice, pitfall olfactometer modified to retain responding beetles by placing a food stimulus (an oat flake) in the glass vials containing the experimental and control stimuli. TheS enantiomer of the pheromone was inactive. Males also produced small amounts of (E)-7-methyl-6-nonen-3-one, (E)-7-methyl-6-nonen-3-ol, and (6E)-7-methyl-3-propyl-2,6-nonadienyl acetate, but these compounds were inactive in the laboratory bioassay. Segregated males and females both produced (R)-(–)-1-octen-3-ol, which by itself was repellent to both sexes but did not diminish beetle response to the aggregation pheromone.Coleoptera: Cucujidae.Research supported by the Natural Sciences and Engineering Research Council of Canada, Strategic Grant G1039 and Operating Grants A3881 and A3706.     

Novel type of sex pheromone structure identified fromStigmella malella (Stainton) (Lepidoptera: Nepticulidae)

Short-chain unsaturated chiral methyl carbinols are identified as a new class of lepidopteran pheromone components. The natural female-produced pheromone of the banded apple pigmyStigmella malella (=Nepticula malella) (Stainton) (Lepidoptera: Nepticulidae) was identified to be a mixture of (S)-(E)-6,8-nonadien-2-ol and (S)-(Z)-6,8-nonadien-2-ol. For monitoring traps, a 10:3E:Z blend at 100–1000 µg is recommended. It is suggested that pheromones with similar structures may be specific to Nepticulidae and other related microlepidopteran families.