Inhibition of male response of drugstore beetles to stegobinone by its isomer

Stegobinone, (2S, 3R, 1R)-2,3,-dihy dro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one, the sex pheromone of drugstore beetles (Stegobium paniceum L.), elicited the pheromonal response from the males of the species in our bioassay system; however, the synthesized diastereomeric mixture of this compound was actually inactive to the males. Although the stegobinone isolated from the beetles of this species had significant activity, its enantiomeric [(±)-2S,3R,1S-] and diatereomeric [(±)-2S,3S,1RS-] isomers were inactive. Adding the (±)-2S,3R,1S isomer to stegobinone significantly reduced the male response. Furthermore, the activity of Stegobinone vanished on keeping it at room temperature for two weeks. In such a stored stegobinone sample, the presence of 2S,3R,1S isomer, the inhibitory component, was confirmed. This isomer might be produced by C-1 epimerization during storage.     

Lasioderma chemistry sex pheromone of cigarette beetle (Lasioderma serricorne F.)

A chemical study of the sex pheromone of the cigarette beetle was carried out. Seven components were isolated from active fractions of column chromatography of the female extract, and their structures were elucidated by spectroscopic evidence and confirmed by synthesis to be (4S,6S,7S)-4,6-di-methyl-7-hydroxynonan-3-one (serricornin) (I), 2,6-diethyl-3,5-dimethyl-3,4-dihydro-2H-pyran (anhydroserricornin) (II), 4,6-dimethylnonan-3,7-dione (III), 4,6-dimethylnonan-3,7-diol (IV), 4,6-dimethyl-7-hydroxy-4-nonen-3-one (V), (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(l-methyl-2-oxobutyl)-4H-pyran-4-one (serricorone) (VI) and (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2-hydroxybutyl)-4H-pyran-4-one (serricorole) (VII).These structural features suggested that the occurrence of these components might be related to the polyketide biosynthesis. The behavioral bioassay and BAG experiments revealed the biological role of each component in the copulatory behavior of this insect.     

Female sex pheromone of the common furniture beetleAnobium punctatum (Coleoptera: Anobiidae): Extraction,identification, and bioassays

Observations and reports on the common furniture beetleAnobium punctatum suggested that, on emergence, females use a sex pheromone to attract males. GLC analysis of ovipositor extracts showed the presence of a single component, which was found to be active by EAG and coupled GLC-EAG techniques, and to attract males in both walking and flying assays. The pheromone was identified by GC-MS as 2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one (stegobinone), which is the sex pheromone of another anobiid, the drugstore beetle,Stegobium paniceum. MaleA. punctatum responded equally to ovipositor extracts of either species, at both the sensory (EAG) and behavioral levels, which poses the question as to how species specificity in mate attraction is achieved.     

Conformational analysis of serricornin: Application of molecular mechanics calculations to stereochemical assignment of serricornin,sex pheromone of cigarette beetle (Lasioderma serricorne F.)

Conformational analysis using molecular mechanics (MM) was performed for a determination of the stereochemistry of serricornin, the sex pheromone of the cigarette beetle (Lasioderma serricorne F.). An exhaustive conformational analysis using MM2 calculations with algorithms for covering torsional energy surfaces of flexible molecules furnishes coordinates and steric energies of all local energy minimum conformers of serricornin, both acyclic and the corresponding cyclic forms. These coordinates gave angles required for the calculation of vicinal H/H coupling constants (³ J _HHs) of each energy minima by Altona's modified Karplus equation. The Boltzmann distributions of all local energy minima were calculated from their steric energies to furnish populations of each energy minimum conformer. Populationweighted averaged³ J _HHs of four enantiomeric pairs, (S ^*,S ^*,S ^*)-, (S ^*,S ^*,R ^*)-, (S ^*,R ^*,S ^*)-, and (R ^*,S ^*,S ^*)-serricornins were calculated from the data above. The observed³ J _HHs of the naturally occurring serricornin, both acyclic and cyclic forms, are fitted best to calcd.³ J _HHs of (4S ^*, 6S ^*, 7S ^*)-acyclic and (3S ^*, 5S ^*, 6S ^*)-cyclic serricornin, respectively, among those of four enantiomeric pairs of serricornin.     

Evidence for a short-range sex pheromone in female Maladera matrida beetle

Laboratory studies with live and frozen Maladera matrida female and male beetles showed that males were attracted to chemical substances emanating from the females at dusk. Beetles exhibited sexual activity (including mating) at dusk towards frozen females but not towards frozen males. Frozen females that had been extracted with methanol together with either hexane or dichloromethane or with a mixture of all three solvents did not elicit male sexual activity. Activity was fully restored when a concentrate of the extract was applied to the previously extracted frozen females. Males also responded with vigorous sexual activity to frozen males to which female extract had been applied. Deterrent chemicals appear to be absent from the male body. Males exposed to females that had been frozen during the morning displayed weak sexual activity, indicating that females lack active semiochemicals. Differences between dusk and morning extracts were found with respect to more than 20 compounds, some of which were present in much higher concentrations at dusk than in the morning, while others were not detected in the morning extract. The active component(s) of the short-range sex pheromone of female M. matrida is (are) presumably to be found among these compounds.     

Aggregation pheromone of coconut rhinoceros beetle,Oryctes rhinoceros (L.) (coleoptera: Scarabaeidae)

Male coconut rhinoceros beetles,Oryctes rhinoceros (L.), produce three sex-specific compounds, ethyl 4-methyloctanoate, ethyl 4-methylheptanoate, and 4-methyloctanoic acid, the first of which is an aggregation pheromone. Synthesis of these compounds involving conjugate addition of organocuprates to ethyl acrylate is reported. In field trapping experiments, (4S)-ethyl 4-methyloctanoate and the racemic mixture were equally attractive and 10 times more effective in attracting beetles than ethyl chrysanthemumate, a previously recommended attractant. Ethyl 4-methylheptanoate was as attractive as ethyl chrysanthemumate and more attractive than 4-methyloctanoic acid, but further studies are required before it can be classed as an aggregation pheromone. Compared to ethyl 4-methyloctanoate alone, combinations of the three male-produced compounds did not increase attraction, whereas addition of freshly rotting oil palm fruit bunches to pheromone-baited traps significantly enhanced attraction. With increasing dose, captures ofO. rhinoceros increased, but doses of 6, 9, and 18 mg/day were competitive with 30 mg/day lures. Newly designed vane traps were more effective in capturing beetles than were barrier or pitfall traps. Results of this study indicate that there is potential for using ethyl 4-methyloctanoate in operational programs to controlO. rhinoceros in oil palm plantations.     

Identification of female-produced sex pheromone from banded cucumber beetle,Diabrotica balteata leconte (Coleoptera: Chrysomelidae)

A sex pheromone produced by female banded cucumber beetle adults,Diabrotica balteata LeConte, was isolated from volatiles trapped on Porapak Q and identified as 6,12-dimethylpentadecan-2-one. The structure was elucidated by spectroscopic analyses and confirmed by synthesis. The synthesized racemic compound was equal to the purified natural pheromone in eliciting responses by banded cucumber beetle males to field traps. A doseresponse characteristic was demonstrated for the racemic material formulated on filter paper or rubber septa and placed in field traps. The absolute configuration at the C-6 and C-12 positions was not established.This article reports the results of research only. Mention of a proprietary product does not constitute an endorsement or the recommendation for its use by USDA.This research was initiated by Dr. P.L. Guss, deceased, Research Chemist, Northern Grain Insects Research Laboratory, ARS, USDA, Brookings, South Dakota. Dr. Guss conducted the preliminary purifications and bioassays that led to the isolation and identification of this pheromone.     

Methylbutynol effectively replaces methylbutenol,a pheromone component ofIps typographus (L.) (Coleoptera: Scolytidae)

In field experiments in Sweden, the constituent 2-methyl-3-buten-2-ol of the aggregation pheromone of the spruce bark bettleIps typographus (L.) was effectively replaced by 2-methyl-3-butyn-2-ol.     

Female-produced oviposition deterrents of the cigarette beetle,Lasioderma serricorne (F.) (Coleoptera: Anobiidae)

Oviposition deterrents of the cigarette beetle,Lasioderma serricorne, were isolated from its adult body extract and found to be identical to (2S,3R,1'S)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(l-methyl-2-oxobutyl)-4H-pyran-4-one (-serricorone) and its lR-epimer (-serricorone) by spectroscopic evidence. Serricorone was previously found as one of the minor sex pheromone components of the same insect, and hence indicating bi-functional nature. The presence of two isomers in the body was proved by careful treatment. Each of them exhibited the same level of oviposition deterring activity, which was less potent than the crude body extract at an increased concentration.     

Studies on the isolation and bioassay of the sex pheromone of the drugstore beetle,Stegobium paniceum (Coleoptera: Anobiidae)

Females ofStegobium paniceum (L.) produce a sex pheromone that causes an excitation and attraction of the males. Male response was highest 5–12 days after adult emergence. Pheromone titer of unmated females increased steadily after 1 day, reached a plateau after 5 days, and continued until at least 14 days. Mature males showed a threshold responsiveness of 3 × 10^?7 μg pheromone. The pheromone titer per female ranged from 50 to 200 ng. On the basis of a high-resolution mass spectrum the empirical formula of the pure isolated pheromone molecule was determined to be C₁₃H₂₀O₃. The pheromone was further defined by its Chromatographic behavior and spectroscopic properties.     

Sex pheromone communication in the odd beetle,Thylodrias contractes motschulsky (Coleoptera: Dermestidae)

Adult virgin females of the odd beetle,Thylodrias contractus, produce a volatile sex pheromone that influences the behavior of conspecific males and attracts them in laboratory olfactometer tests. The active substance can be collected by allowing virgin females to walk on absorbent paper disks. Disks exposed to mated females do not elicit a response from males. The male odd beetle repeatedly rubs the antennae, head, and thorax of a female with a setate glandular area on his second abdominal sternum during courtship, probably secreting a reciprocally active aphrodisiac substance.Journal Paper No. J-10248 of the Iowa Agriculture and Home Economics Experiment Station, Ames, IA 50011. Project No. 2259.     

(R)-acetoin-female sex pheromone of the summer chafer Amphimallon solstitiale (L.)

Extracts of Amphimallon solstitiale (L.), a well known, widely distributed and rather common European scarab beetle, were analyzed by GC-MS and GC-EAD. Acetoin -(R):(S) < 9:1 - as well as 2,3-butanediol -(2R,3R):(2S,3S) :meso = 1:1:9 - were present in extracts of both males and females. Although (2S,3S)-butanediol did not show any EAD activity, the other compounds elicited strong responses exclusively with male antennae. In contrast, several EAD active green leaf volatiles were detected equally well by male and female antennae. During preliminary field bioassays, (R)-acetoin was highly attractive to swarming males, whereas neither rac-acetoin nor the 2,3-butanediols showed activity. Therefore, (R)-acetoin is the female sex pheromone of A. solstitiale.     

Identification and synthesis of female sex pheromone of Oriental beetle,Anomala orientalis (Coleoptera: Scarabaeidae)

Females of the Oriental beetle,Anomala orientalis (Waterhouse), release a sex pheromone composed of a 9:1 blend of (Z)- and (E)-7-tetradecen-2-one. The double-bond position of the pheromone was determined by DMDS derivatization and interpretation of the fragmentation patterns produced by monounsaturated ketones. In a sustained-flight tunnel, males responded by flying toward female beetles and attempting to copulate with them. Both effluvium and whole-body extracts of OB females were analyzed, and the activity was found only in the airborne extracts. Flight-tunnel bioassays also showed that a synthetic 90:10Z/E blend on a rubber septum was attractive and that the responses of males to this blend were equivalent toZ isomer alone, but much better than to the singleE isomer.     

A new component of the female sex pheromone ofBlattella germanica (L.) (Dictyoptera: Blattellidae) and interaction with other pheromone components

A fourth component, 3,11-dimethyi-2-heptacosanone, was identified as a cuticular contact sex pheromone of the female German cockroach,Blattella germanica. In behavioral assays, higher dosages of 3,11-dimethyl-2-heptacosanone were needed to elicit similar sexual responses in males to those elicited by the major pheromone component, 3,11-dimethyl-2-nonacosanone. A 1585 blend of the C₂₇ and C₂₉ methyl ketone homologs resulted in a dose-response curve intermediate between that of each of the components alone, indicating independence of activity of each component and lack of synergism. Moreover, the activity of 3,11-dimethyl-2-nonacosanone was not enhanced by female cuticular hydrocarbons. The relationship between sexual responses of males to females and to isolated female antennae, and the amount of cuticular pheromone on whole females was investigated. Cuticular sex pheromone found on females increased with the age of the female, as did the male response to whole females. However, a bimodal male response was elicited by isolated female antennae. Differences between behavioral and analytical assays of pheromone are discussed.     

Interactions of pheromone component odor plumes of western pine beetle

The relationships between catch ofD. brevicomis LeC. at sources of the synergistic pheromone components,exo-brevicomin (E) and frontalin (F), and increasing distance of separation of sources were investigated in the forest. The two components were each released with the host monoterpene, myrcene (M), in trap pairs. The traps of each pair were spaced apart at various distances (0–16 m) in either horizontal or vertical lines that were perpendicular to the mean wind direction. Both sexes were most strongly attracted when the two components were released from the same source, and increasing distance of separation between components caused exponential decreases in trap catch for all trap configurations. Males were significantly more attracted to traps with E, M alone than to corresponding traps with F, M alone, while females exhibited a preference for F, M. The theoretical relationships and properties of two coalescing plumes of individual components and their intersecting active space are presented and discussed. It is proposed that confusion or communication disruption techniques for insect control may be more successful if components are released individually from many points rather than released similarly in blends. Dendroctonus brevicomis LeC. (Coleoptera: Scolytidae).Supported in part by grants from U.S.A. and Sweden, NSF (INT-8503520), STU (84-3937), NFR, FRN, and SJFR.     

Evidence for a sex pheromone in the hide beetle,Dermestes maculatus (De Geer) (Coleoptera: Dermestidae)

Adults of the hide beetle,Dermestes maculatus (De Geer), were shown to have a female-produced sex pheromone which excited males. Male response was positively correlated with increasing age, but females produced a higher level of pheromone at 6–8 days of age than at younger or older ages. Extractable female pheromone and male response varied over the photophase with peak values that occurred during the latter hours. Quantitative bioassay indicated that the 50% male response level (RD₅₀) would be elicited by a pheromone exposure of 0.01 female equivalents (FE). Females extracted 24 hr after mating had a lower level of extractable pheromone than did virgin females of the same age.Mention of a proprietary product does not constitute an endorsement by the Minnesota Agricultural Experiment Station.     

Identification of a minor component of the sex pheromone ofLeucoptera malifoliella (Lepidoptera,lyonetiidae)

A new minor component in the female volatile extract ofLeucoptera malifoliella (Costa) (Lepidoptera, Lyonetiidae) has been identified as 5,9-dimethyloctadecane (2). The amount detected of the minor compound2 ranged from 4 to 8% in comparison with the major component 5,9-dimethylheptadecane (1). Neither compound has been found in the male volatile extract. The identification has been based on its spectroscopic properties and Chromatographic behavior in comparison with an authentic synthetic sample. The synthesis has been carried out through a short route from 2,6-dimethylcyclohexanone (3). In field tests, compound2 appears to act as a Synergist of the major component1 when mixed with the latter in a 1000.1– 5 ratio.     

Evidence for a sex pheromone in bark beetle parasitoid Roptrocerus xylophagorum

Male Roptrocerus xylophagorum (Ratzeburg) (Hymenoptera: Pteromalidae) exhibited courtship and mating behaviors including wing fanning, antennation, mounting, and copulation attempts when exposed to glass bulb decoys coated with a whole-body extract of females in hexane, acetone, or methanol. Activity of extract-treated decoys declined gradually over one week. Males responded much less strongly to freeze-killed female cadavers extracted with solvents than to unextracted cadavers; treatment of extracted cadavers with female extract restored male responses. The pheromone was found to be equally present over the surface of both the abdomen and head/thorax of females, and the origin of the pheromone could not be conclusively localized to any single body region. The activity of pheromone on females increased between day 1 and days 3–5 following eclosion; otherwise, pheromone activity was not significantly affected by either female age or mating. Males were arrested within the zone of a glass surface on which females had walked, suggesting that the pheromone might be substrate-borne. Recent exposure to females reduced male responsiveness, but responsiveness was fully restored after a few hours of male isolation from females. When hexane extracts of whole females were fractionated on silica gel, the pheromone's activity was largely recovered with the first, most nonpolar fraction. Female extracts and fractions were analyzed by coupled gas chromatography–mass spectrometry. Cuticular hydrocarbon alkanes were identified as the extract components whose concentrations correlated best with male responses. Evidence of the pheromone's long persistence, low volatility, low polarity, and presence over the insect's entire body surface further supported the hypothesis that the pheromone was composed of one or more cuticular hydrocarbons.     

Reinvestigation of anhydroserricornin, (2S,3S)-2,6-diethyl-3,5-dimethyl-3,4-dihydro-2H-pyran,as a sex pheromone component for male cigarette beetle

Reinvestigation of the pheromonal activity of anhydroserricornin, (2S,3S)-2,6-diethyl-3,5-dimethyl-3,4-dihydro-2H-pyran, showed that the magnitude of its activity was less than 1/10³ of that of serricornin, 7-hydroxy-4,6-dimethyl-3-nonanone, the sex pheromone of the cigarette beetleLasioderma serricorne (F.). Neither a synergistic nor an inhibitory effect of anhydroserricornin addition on the action of serricornin was observed.     

Identification of sex pheromone of tomato pinworm,Keiferia lycopersicella (Wals.)

A sex pheromone produced by femaleKeiferia lycopersicella (Walsingham) was isolated and identified as (E)-4-tridecenyl acetate, based on chemical analyses, electroantennogram assays, and field trapping in California and Florida. Males were captured equally well in traps baited with (E)-4-tridecenyl acetate alone or a variety of (Z)- and (E)-4-tridecenyl acetate blends, although theZ isomer was not detected in extracts of female glands.Lepidoptera: Gelechiidae.