Diolefin analog of a sex pheromone component ofHeliothis zea active in disrupting mating communication

Summary A hydrocarbon (Z)-1, 12-heptadecadiene, was synthesized from the major sex pheromone of the corn earworm,Heliothis zea (Boddie). In field tests, significant disruption of the sexual behavior ofH. zea males was obtained, comparable to the pheromone (Z)-11-hexadecenal. This novel diolefin should be inexpensive, exhibit improved stability, and may lead to improved methods of control.Reprint requests to D.E. Weidhaas, P.O. Box 14565, Gainesville (FL 32604, USA).     

Avoidance of competition by spruce bark beetles,Ips typographus andPityogenes chalcographus

Bark beetles,Ips typographus andPityogenes chalcographus, attracted by synthetic or natural pheromone to Norway spruce logs,Picea abies, preferred to colonize uninfested logs rather than logs occupied by these beetles, probably as a means of avoiding intra-and interspecific competition. The aggregation pheromone components ofP. chalcographus, chalcogran and methyl (E, Z)-2,4-decadienoate, inhibited the attraction response ofI. typographus to its pheromone components (methyl butenol andcis-verbenol), while the converse was not true. However, verbenone released from colonized bark inhibited pheromonal response ofP. chalcographus.     

Determination of diel periodicity of sex pheromone release in three species of Lepidoptera by ‘closed-loop-stripping’

Summary By means of closed-loop-stripping and subsequent GC analyses the diel periodicity of release of (Z)-11-hexadecenyl acetate, (E)-8-dodecenyl acetate, and (Z)-9-tetradecenyl acetate, the main constituents of the respective sex pheromone blends ofMamestra brassicae, Cryptophlebia leucotreta andSpodoptera sunia females, was determined.Pheromones, 64. For the 63rd contribution we have taken from: Szöcs, G., Toth, M., Bestmann, H. J., Vostrowsky, O., Heath, R. R., and Tumlinson, J. H., Z. Naturforsch.42c (1987) 165; Pheromones, 62: Bestmann et al.¹³.     

Acyl fluorides as reactive mimics of aldehyde pheromones: hyperactivation and aphrodisiac inHeliothis virescens

Summary Substitution of fluorine for the aldehydic hydrogen provides behaviorally active, chemically reactive pheromone mimics. In male moths of the tobacco budwormHeliothis virescens, Z9–14:Acf and Z11–16:Acf cause hyperactivity and irreversible extension of the genitalia in over 80% of treated moths. In addition, a combination of the two components leads to 10–50% of the pairs involving one treated partner becoming locked in copula.Supported by NSF grant PCM-8112755 and DMB-8316931, by a Fellowship from the Alfred P. Sloan Foundation (1981–85), and by Teacher-Scholar Grant from the Camille and Henry Dreyfus Foundation (1981–86) to G.D.P. Address correspondence to G.D.P.     

Methoxymercuration-demercuration and mass spectrometry in the identification of the sex pheromones ofPanolis flammea,the pine beauty moth

Summary The major components of the sex pheromone system ofPanolis flammea, pine beauty moth have been identified as (Z)-9-tetradecenyl acetate, (Z)-11-hexadecenyl acetate and (Z)-11-tetradecenyl acetate in the ratio 10051; the double bond position of these derivatives was established by microscale application of a methoxymercuration-demercuration technique and GC-MS followed by multiple ion monitoring.We thank the Science Research Council and Forestry Commission for financial support. We are grateful for the collaboration of Messrs Stoakley and Bevan, Dr C. Longhurst and Mrs J. Edwards.     

Regulatory steps in sex pheromone biosynthesis inMamestra brassicae L. (Lepidoptera: Noctuidae)

Summary The de novo biosynthesis of (Z)-11-hexadecenyl acetate, the most abundant pheromone component inM. brassicae, starting from acetate via palmitic acid, requires the presence of a pheromone-biosynthesis-activating neurohormone. Moreover, the conversion of palmitic acid to (Z)-11-hexadecenyl acetate is strongly dependent on the presence of the neurohormone. However, no significant dependence was found for the conversion of (Z)-11-hexadecenoic acid to (Z)-11-hexadecenyl acetate. This indicates that the neurohormonal control of pheromone biosynthesis inM. brassicae occurs at the level of palmitic acid.     

Bombykol biosynthesis from deuterium-labeled (Z)-11-hexadecenoic acid

Summary (Z)-[11,12d ₂]-11-Hexadecenoic acid was applied topically to the pheromone gland of silkworm pupa. After eclosion, the gland components were analyzed by capillary GC-MS. (Z)-11-Hexadecenoic acid, a characteristic fatty acid of the gland, was found to be a precursor of bombykol, (Z)-11-hexadecenol and bombyk acid.We are greatful to Dr Y. Tamaki and Mr H. Sugie of the National Institute of Agricultural Science for mass spectrometric analysis and Dr M. Noda of Kyoto Prefectural University for valuable discussion. This work was supported by a Grant-in-aid for Scientific Research (to K.H. No. 56112011) from the Ministry of Education, Science and Culture of Japan.     

Host race pheromone polymorphism in the larch budmoth

Summary Analysis of the sex gland content ofZeiraphera diniana females and field responses of males to synthetic compounds show that the sympatrically occurring food specialists on various coniferous hosts use different blends ofE-9-dodecenyl acetate andE-11-tetradecenyl acetate as sex pheromones.This research was supported by the Swiss National Science Foundation. Contribution No. 116 of the Working Group for the Study of the Population Dynamics of the Larch Budmoth.     

Field testing ofcis-11-tetradecenal as attractant or synergist in tortricinae

Summary Field studies have shown thatcis-11-tetradecenal is an effective attractant for maleChoristoneura conflictana, a pest of aspen. These studies also indicate thatcis-11-tetradecenal is probably a secondary component in the sex pheromone systems ofChoristoneura rosaceana andChoristoneura fumiferana.Christoneura conflictana (Wlk.),C. rosaceana (Harris) andC. fumiferana (Clemens) (Lepidoptera: Tortricidae: Tortricinae).Contribution No. IPRI 296.     

Chemical analysis of the pheromone blends produced by males and females of the neotropical moth,Mocis megas (Guénée) (Lepidoptera,Noctuidae, Catocalinae)

Summary Pheromonal secretions produced by females and males of the noctuid moth,Mocis megas (Guénée) have been analyzed by gas chromatography and mass spectrometry (EI (electron impact) and CI (chemical ionization)). The female sex pheromone was a blend of (Z,Z,Z) 3,6,9 heneicosatriene (55%) and (Z,Z) 3,6-cis-9S, 10R-epoxyheneicosadiene (45%). Male secretion produced at the level of a prothoracic organ was a blend of two unsaturated major hydrocarbons: (Z,Z) 6,9 heneicosadiene, (64%) and (Z,Z,Z) 3,6,9 heneicosatriene (24%) and C₁₉, C₂₀ and C₂₂ homologues (total ratio 12%), as minor components. The trienic hydrocarbon was present in both sexes. The behavioral role of this male secretion has not yet been elucidated.     

Confirmation of sex pheromone biosynthesis from (16-D3)palmitic acid in the turnip moth using capillary gas chromatography

Summary (16-D₃)palmitic acid was applied topically to pheromone glands of the turnip moth. After incubation omega labeled analogues of fatty acid methyl esters and acetates were identified by gas chromatography with flame ionization detection and selected ion monitoring. The pheromone components (Z)-5-decenyl, (Z)-7-dodecenyl- and (Z)-9-tetradecenyl acetate were all biosynthesized from palmitic acid along a common pathway.     

Marine eicosanoids: Occurrence of 8-(R)-HETE in the starfishPatiria miniata

Summary The first isolation of 8-(R)-hydroxy-5Z, 9E, 11Z, 14Z-eicosatetraenoic acid [8-(R)-HETE] from a marine source, the pacific starfishPatiria miniata, is reported. 8-(R)-HETE occurs together with 8-(R)-hydroxy-5Z, 9E, 11Z, 14Z, 17Z-eicosapentaenoic acid.     

Sex pheromone conversion and degradation in antennae of the silkworm mothBombyx mori L.

Summary In living antennae of the silkworm mothBombyx mori L. the pheromone compound (E, Z)-10,12-hexadecadienol and hexadecanol are enzymatically converted to their corresponding fatty aldehydes, acids and long-chain fatty acid esters. The pheromone is completely degraded at high rates in the antennae of freshly hatched moths. The polar volatile [³H]metabolites exclusively consist of tritiated water. The half-life of the pheromone is about 2.5 min in males and 0.5 min in females. Drying inactivates the enzymes responsible for pheromone oxidation.Dedicated to Professor Adolf Butenandt on the occasion of his 85th birthday     

On the specific attraction of the males of the six-toothed spruce bark beetle,Pityogenes chalcographus (L.) to a mixture of synthetic pheromones of the eight-toothed spruce bark beetle,Ips typographus (L.) (Coleoptera,Scolytidae)

Summary Traps containing a mixture of attractants forIps typographus also caught other species of bark beetles. The numbers ofPityogenes chalcographus, Pityogenes conjunctus, andTrypodendron lineatum were too high to be interpreted as accidental captures. The males of the polygamousP. chalcographus were specifically attracted, indicating that theI. typographus pheromone or one of its components acts as a kairomone and primary attractant for the pioneering males ofP. chalcographus.     

Trail pheromone of the red imported fire antSolenopsis invicta (Buren)

Summary Z,Z,Z-Allofarnesene (2Z, 4Z, 6Z)-2,6,10-trimethyl-2, 4, 6, 10-dodecatetraene) was identified as the trail pheromone of the red imported fire ant by comparing chromatographic and spectral properties of the pheromone obtained from ant Dufour's glands with those of synthetic compounds.Approved as TA 16297 by the director of the Texas Agricultural Experiment Station. Supported by the Texas Department of Agriculture Interagency Contract IAC-0459 (79-81).     

Stimulation der Eiablage unbegatteter Weibchen des MondspinnersActias selene durch ein Männchen-Pheromon

Summary Mated females ofActias selene lay their eggs quicker than virgin females. Of the latter, virgins kept isolated in a separate room lay their eggs later than virgins kept in a room where males are present. Antennaless virgin females kept in the same room as males behave like isolated virgin females. It is concluded that the males produce an olfactory active sex pheromone that stimulates oviposition in females.     

The male pheromone of the old house borerHylotrupes bajulus (L.) (Coleoptera: Cerambycidae): Identification and female response

We report here the identification of the long-range, male-produced sex pheromone of the Old house borerHylotrupes bajulus. Chemical analysis of hexane extracts obtained by surface extraction from dissected prothoracic glands and from headspace samples of the two sexes, revealed male-specific compounds: (3R)-3-hydroxy-2-hexanone, 2-hydroxy-3-hexanone, the diastereomeric diols (2R, 3R)-2,3-hexanediol and (2S, 3R)-2,3-hexanediol, 2,3-hexanedione, as well as 1-butanol.In wind tunnel bioassays we tested the influence of these male-specific compounds from the prothoracal glands on the behaviour of unmated and mated females. Specific behavioural sequences of the tested females (activity, running behaviour, searching, cleaning, flying, extension of ovipositor) were recorded. Unmated females were attracted by male beetles, headspace extracts of males, synthetic blends of the major pheromone compounds as well as by the components (3R)-3-hydroxy-2-hexanone, and the diastereomeric diols. Hexane, female beetles and 2,3-hexanedione did not attract unmated females. The reactions of mated females to male beetles and headspace samples did not differ significantly from those of the controls.The results of the bioassays show that the two-stage premating behaviour is initiated by emission of a long-range sex pheromone from the male prothoracal glands, which functions as an activator, attractant, and possibly aphrodisiac for unmated females.     

Female sex pheromone of the longhorn beetleMigdolus fryanus Westwood: N-(2′S)-methylbutanoyl 2-methylbutylamine

The first known long-range female-released sex pheromone for the family Cerambycidae is reported fromMigdolus fryanus, a sugarcane pest in South America. Although two female-specific compounds, namely, N-(2S)-methylbutanoyl 2-methylbutylamine and N-formyll-isoleucine methyl esters were identified, field tests with synthetic chemicals revealed that only the amide was active and that the amino acid derivative neither increased or decreased trap catches by the amide. This is the first identification of amide as a sex pheromone.     

Mating attempts between the Scarlet Tiger Moth,Callimorpha dominula L., and the Cinnabar Moth,Tyria jacobaeae L. (Lepidoptera: Arctiidae), involve a common sex pheromone composition

It has been suggested that a common sex pheromone composition may account for interspecific sexual interactions observed with certain moths in the Arctiidae. In this study, it is demonstrated that the sex pheromones released by females of the Scarlet Tiger Moth,Callimorpha dominula L., and the Cinnabar Moth,Tyria jacobaeae L., have similar activities and elute at the same retention time on analysis by coupled gas chromatography (GC)-electrophysiology with males from each species. Peak enhancement on GC, chiral GC and coupled GC-mass spectrometry using authentic compounds show that the sex pheromone for bothC. dominula andT. jacobaeae is (3Z,6Z,9S,10R)-9,10-epoxyheneicosa-3,6-diene.     

Increased pheromone catabolism by antennal esterases after adult eclosion of the cabbage looper moth

Summary A marked increase in pheromone hydrolysis by antennal esterases occurred 24–72 h after eclosion and was coincident with the age ofTrichoplusia ni (Hübner) males that were maximally responsive to the pheromone as indicated from previous reports. This observed hydrolytic activity was also accompanied by the appearance of 3 esterase bands in the electrophoretic patterns of the antenna. The finding thus lends support to the hypothesis that the observed pheromone catabolism is an event closely associated with the olfaction process.Employed through a cooperative agreement with the Insect Attractants, Behavior, and Basic Biology Research Laboratory, Agricultural Research, Science and Education Administration, USDA, Gainesville, FL 32604.The authors acknowledge Dr James L. Nation for his helpful comments during the course of the work.