Male-Produced Sex Pheromone of Tibraca limbativentris Revisited: Absolute Configurations of Zingiberenol Stereoisomers and their Influence on Chemotaxis Behavior of Conspecific Females.

The rice stalk stink bug, Tibraca limbativentris, is an important rice pest in Brazil with a high invasive potential for Mexico and the USA. The sex pheromone of this species was previously identified as a combination of two stereoisomers of 1,10-bisaboladien-3-ol (zingiberenol), but the absolute configurations of these sesquiterpenes were not determined, neither were their effect(s) on T. limbativentris behavior evaluated. In this study, using two chiral columns, we compared retention times of the two natural 1,10-bisaboladien-3-ol stereoisomers from air-entrainment samples of male T. limbativentris with those of synthetic stereoisomers of 1,10-bisaboladien-3-ol. The results showed that T. limbativentris males produce (3S,6S,7R)-1,10-bisaboladien-3-ol (1) and (3R,6S,7R)-1,10-bisaboladien-3-ol (5) as their sex pheromone. Two new minor, male-specific components were also identified as cis and trans isomers of 2,10-bisaboladien-1-ol (sesquipiperitol). Y-tube olfactometer bioassays showed that the major (3S,6S,7R) isomer 1 was essential for attraction of T. limbativentris females, but the minor (3R,6S,7R) isomer 2 was not, nor did it show synergistic/antagonistic effects when added to the major isomer. The (1S,6S,7R) and (1R,6S,7R) stereoisomers of sesquipepiritol also attracted T. limbativentris females.

Trap Cropping Systems and a Physical Barrier for Suppression of Stink Bugs (Hemiptera: Pentatomidae) in Cotton.

Euschistus servus (Say), Nezara viridula (L.), and Chinavia hilaris (Say) (Hemiptera: Pentatomidae) are economic pests of cotton in the coastal plain of the southeastern United States. The objective of this 2-yr study was to determine the ability of trap cropping systems, pheromone-baited stink bug traps, and a synthetic physical barrier at the peanut-to-cotton interface to manage stink bugs in cotton. The physical barrier was the most effective management tactic. Stink bug density in cotton was lowest for this treatment. In 2010, boll injury was lower for the physical barrier compared to the other treatments except for soybean with stink bug traps. In 2011, boll injury was lower for this treatment compared to the control. Soybean was an effective trap crop, reducing both stink bug density in cotton and boll injury regardless if used alone or in combination with either stink bug traps or buckwheat. Incorporation of buckwheat in soybean enhanced parasitism of E. servus egg masses by Telenomus podisi Ashmead in cotton. The insertion of eyelets in the lid of the insect-collecting device of a stink bug trap allowed adult stink bug parasitoids, but not E. servus, to escape. Stand-alone stink bug traps were not very effective in deterring colonization of cotton by stink bugs or reducing boll injury. The paucity of effective alternative control measures available for stink bug management justifies further full-scale evaluations into these management tactics for control of these pests in crops.

Pheromone attraction and cross-attraction of Nezara, Acrosternum, and Euschistus spp. stink bugs (Heteroptera: Pentatomidae) in the field.

Detecting infestations of stink bugs (Heteroptera: Pentatomidae) using pheromones remains problematic, particularly so in the United States for the exotic stink bug, Nezara viridula L., and our native stink bug, Acrosternum hilare (Say). Therefore, we conducted a 2-yr on-farm study to examine the attractiveness and possible cross-attraction of the reported pheromones for N. viridula and A. hilare and those previously discovered for Euschistus servus (Say) and Plautia stali Scott to N. viridula, A. hilare, and E. servus. The attractiveness of selected pentatomid pheromones to tachinid parasitoids of stink bugs was also examined. We showed for the first time under field conditions that N. viridula can be trapped with its reported pheromone, a 3:1 trans- to cis-(Z)-alpha-bisabolene epoxide blend. In fact, attraction of N. viridula increased with higher pheromone doses. Traps baited with a 5:95 trans- to cis-(Z)-alpha-bisabolene epoxide blend, the reported male-produced A. hilare attractant pheromone, failed to attract significantly more A. hilare than did unbaited control traps. Instead A. hilare was significantly cross-attracted to the P. stali pheromone [methyl (E,E,Z)-2,4,6-decatrienoate]. The E. servus pheromone [methyl (E,Z)-2,4-decadienoate], either alone or in combination with P. stali pheromone, was more attractive to E. servus than to N. viridula, P. stali, or A. hilare pheromones. In general, tachinid parasitoids were found responsive to the male-specific volatiles of their known hosts, including the attractiveness of Trichopoda pennipes (F.) to sesquiterpenoid blends characteristic of A. hilare and N. viridula. A tachinid parasitoid of E. servus, Cylindromyia sp., seemed to be attracted to E. servus pheromone. In conclusion, our results indicate that stink bug traps baited with lures containing N. viridula pheromone blend, P. stali pheromone, and E. servus pheromone have the greatest potential for detecting populations of N. viridula, A. hilare, and E. servus, respectively, in diversified agricultural landscapes.

Saturated and monofluoro analogs of the oriental fruit fly attractant methyl eugenol show reduced genotoxic activities in yeast.

Methyl eugenol, is a commercially used fruit fly attractant and a suspected carcinogen. Several phenylpropenes, including methyl eugenol and the known carcinogen safrole, score negative in the Salmonella assay but score positive in the yeast DEL assay that selects for intrachromosomal recombination events in the yeast Saccharomyces cerevisiae. In an attempt to dissociate the beneficial properties of methyl eugenol from its genotoxic properties, saturated or fluorinated analogs were evaluated for their ability to induce intrachromosomal (DEL) recombination in yeast. Field tests have previously shown that all of the analogs used have appreciable properties as fruit fly attractants. The analogs 1,2-dimethoxy-4-ethylbenzene, 1,2-dimethoxy-4-(2-fluoro-2-propenyl)benzene, 1,2-dimethoxy-4-(2-fluoroethyl)benzene and 1,2-dimethoxy-4-(3-fluoro-2-propenyl)benzene all showed reduced toxicity and reduced recombinagenicity in yeast compared to methyl eugenol. These results confirm the validity of fluorination and/or removal of the 2-propenyl moiety in reducing the toxicity and recombinagenicity of methyl eugenol derivatives.

Synthesis of attractants for oriental fruit flyDacus dorsalis Hendel using a catalytic organocopper coupling reaction.

A general synthetic approach to various catechol derivatives was developed using a copper-catalyzed cross-coupling reaction of 1,2-dimethoxy-4-brornomethyl, 1-ethoxy-2-methoxy-4-bromomethyl- and 2-ethoxy-1-methoxy-4-bromomethylbenzenes with Grignard reagents. Dilithium tetrachlorocuprate was an acceptable catalyst in the dimethoxy series, whereas copper(I) iodide in THF-HMPA was a superior catalyst in all cases due to decreased side reactions, i.e., reduction and reductive coupling. Methyl-substituted analogs of methyl eugenol, a potent attractant of Oriental fruit fly,Dacus dorsalis Hendel, were synthesized by this method and evaluated for attractancy in field tests.