SEMIOCHEMICAL ACTIVITY OF PHEROMONES AND ANALOGUES OF THREE MATSUCOCCUS SPECIES (HEMIPTERA: COCCOIDEA: MATSUCOCCIDAE)

SEMIOCHEMICAL ACTIVITY OF PHEROMONES AND ANALOGUES OF THREE MATSUCOCCUS SPECIES (HEMIPTERA: COCCOIDEA: MATSUCOCCIDAE). The sex pheromone of the Israeli pine bast scale, Matsucoccus josephi Bodenheimer Harpaz (Homoptera: Matsucoccidae), was identified as the ketone (2E,5R,6E,8E)-5,7-dimethyl-2,6,8- decatrien-4-one. The chiral diene chain is common also to the sex pheromones of M. matsumurae Bean Godwin and M. feytaudi Ducasse. The species-specificity of the three pheromones is due to the differences in the second side chain of these ketones. Field and GC- EAD studies indicated that the sex pheromones of each of the three Matsucoccus spp. is a potent kairomone of both males and females of the predator Elatophilus hebraicus Pericart (Hemiptera: Anthocoridae). The response of E. hebraicus to the sex pheromones of M. matsumurae and M. feytaudi is particularly interesting since it does not occur in the distribution area of these two congeneric spp. These results prompted us to prepare a series of analogues with variations in the two side chains in order to probe the structure-activity relationship of the pheromonal/kairomonal attractancy of M. josephi and E. hebraicus. Field results indicate that alterations in the common diene moiety affected the kairomonal activity, while structural changes in the second side chain markedly reduced the pheromonal activity. Key words: stereoisomer

Attraction of Planococcus ficus males to racemic and chiral pheromone baits: flight activity and bait longevity

The vine mealybug (VM), Planococcus ficus (Signoret), is a worldwide pest and affects mainly grapevine and figs. In Israel, (S)-lavandulyl senecioate [(S)-LS] and (S)-lavandulyl isovalerate [(S)-LI] were identified from VM reared for several generations on potato sprouts, when compared with the identification of only (S)-LS from feral females. Racemic lavandulyl senecioate (LS) can be used for fieldwork because the unnatural enantiomer is benign and does not affect the activity of the pheromone. Lures loaded with 200 lg of LS remained active for 24 weeks but it is recommended to replace lures after 12 weeks to preserve constant and high attractiveness. Delta sticky traps, baited with 50 or 200 lg of LS were used to determine the daily flight pattern and the seasonal flight activity including vine plant infestation. A positive correlation between peak mealybug density and male capture was observed strengthening the usefulness of the pheromone traps for monitoring the pest. Addition of racemic or the two enantiomers of lavandulyl isovalerate (LI) to LS decreased the capture of VM males. The level of inhibition varied during 2003–2004. Both enantiomers of LI displayed the same antagonistic activity. Addition of (S)-lavandulol to the pheromone resulted in shutdown of the traps. Inhibition by the antipode, (R)-lavandulol, was moderate indicating a certain degree of chiral discriminatio

Mechanismen massenspektrometrischer Fragmentierungsreaktionen, XV. Sterische und konformative Effekte in den Massenspektren von 5-tert-Butyl-1,3-cyclohexandiolen und ihren Methyläthern

Grützmacher H-F, Asche R. Mechanismen massenspektrometrischer Fragmentierungsreaktionen, XV. Sterische und konformative Effekte in den Massenspektren von 5-tert-Butyl-1,3-cyclohexandiolen und ihren Methyläthern. Chemische Berichte. 1975;108(6):2080-2096

Biosynthesis of Unusual Moth Pheromone Components Involves Two Different Pathways in the Navel Orangeworm, Amyelois transitella

The sex pheromone of the navel orangeworm, Amyelois transitella (Walker) (Lepidoptera: Pyralidae), consists of two different types of components, one type including (11Z,13Z)-11,13-hexadecadienal (11Z,13Z-16:Ald) with a terminal functional group containing oxygen, similar to the majority of moth pheromones reported, and another type including the unusual long-chain pentaenes, (3Z,6Z,9Z,12Z,15Z)-3,6,9,12,15-tricosapentaene (3Z,6Z,9Z,12Z,15Z-23:H) and (3Z,6Z,9Z,12Z,15Z)- 3,6,9,12,15-pentacosapentaene (3Z,6Z,9Z,12Z,15Z-25:H). After decapitation of females, the titer of 11Z,13Z-16:Ald in the pheromone gland decreased significantly, whereas the titer of the pentaenes remained unchanged. Injection of a pheromone biosynthesis activating peptide (PBAN) into the abdomens of decapitated females restored the titer of 11Z,13Z-16:Ald and even increased it above that in intact females, whereas the titer of the pentaenes in the pheromone gland was not affected by PBAN injection. In addition to common fatty acids, two likely precursors of 11Z,13Z-16:Ald, i.e., (Z)-11-hexadecenoic and (11Z,13Z)-11,13-hexadecadienoic acid, as well as traces of (Z)-6-hexadecenoic acid, were found in gland extracts. In addition, pheromone gland lipids contained (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-icosapentaenoic acid, which also was found in extracts of the rest of the abdomen. Deuterium-labeled fatty acids, (16,16,16-D3)-hexadecanoic acid and (Z)-[13,13,14,14,15,15,16,16,16-D9]-11-hexadecenoic acid, were incorporated into 11Z,13Z-16:Ald after topical application to the sex pheromone gland coupled with abdominal injection of PBAN. Deuterium label was incorporated into the C23 and C25 pentaenes after injection of (9Z,12Z,15Z)- [17,17,18,18,18-D5]-9,12,15-octadecatrienoic acid into 1–2 d old female pupae. These labeling results, in conjunction with the composition of fatty acid intermediates found in pheromone gland extracts, support different pathways leading to the two pheromone components. 11Z,13Z-16:Ald is probably produced in the pheromone gland by Δ11 desaturation of palmitic acid to 11Z-16:Acid followed by a second desaturation to form 11Z,13Z-16:Acid and subsequent reduction and oxidation. The production of 3Z,6Z,9Z,12Z,15Z-23:H and 3Z,6Z,9Z,12Z,15Z-25:H may take place outside the pheromone gland, and appears to start from linolenic acid, which is elongated and desaturated to form (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-icosapentaenoic acid, followed by two or three further elongation steps and finally reductive decarboxylation

The Chemistry of the Postpharyngeal Gland of Female European Beewolves

Females of the European beewolf, Philanthus triangulum, possess a large glove-shaped gland in the head, the postpharyngeal gland (PPG). They apply the content of the PPG to their prey, paralyzed honeybees, where it delays fungal infestation. Here, we describe the chemical composition of the gland by using combined GC-MS, GC-FTIR, and derivatization. The PPG of beewolves contains mainly long-chain unsaturated hydrocarbons (C23–C33), lower amounts of saturated hydrocarbons (C14–C33), and minor amounts of methyl-branched hydrocarbons (C17–C31). Additionally, the hexane-soluble gland content is comprised of small amounts of an unsaturated C25 alcohol, an unknown sesquiterpene, an octadecenylmethylester, and several long-chain saturated (C25, C27) and unsaturated (C23–C27) ketones, some of which have not yet been reported as natural products. Surprisingly, we found a dimorphism with regard to the major component of the PPG with some females having (Z)-9-pentacosene, whereas others have (Z)-9-heptacosene as their predominant component. The biological relevance of the compounds for the prevention of fungal growth on the prey and the significance of the chemical dimorphism are discussed