| Title: | "Synthesis and characterization of 2,13- and 3,13-octadecadienals for the identification of the sex pheromone secreted by a clearwing moth" |
| Author(s): | Islam A; Yamamoto M; Sugie M; Naka H; Tabata J; Arita Y; Ando T; |
| Address: | "Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan" |
| DOI: | 10.1007/s10886-007-9334-x |
| ISSN/ISBN: | 0098-0331 (Print) 0098-0331 (Linking) |
| Abstract: | "In addition to 2,13- and 3,13-octadecadien-1-ols and their acetates, aldehyde analogs have been identified from lepidopteran species in the family Sesiidae. To establish a reliable analytical method for determining the positions and configurations of the two double bonds in natural pheromone components, all geometric isomers of the 2,13- and 3,13-octadecadienals were synthesized by Dess-Martin oxidation of the corresponding alcohols with limited isomerization of the double bond at the 2- or 3-position. GC-MS analysis of these aldehydes showed isomerization of (Z)-2-, (Z)-3-, and (E)-3-double bonds to an (E)-2-double bond, even with a cool on-column injection. In contrast, HPLC analysis with an ODS column was accomplished without isomerization. The geometric isomers of each dienal eluted in the order ZZ --> EZ --> ZE --> EE. The conjugated 2,13-dienals were detectable in nanogram amounts with a UV detector at 235 nm. Whereas the detection of 3,13-dienals was difficult because of the lack of a chromophore, a highly sensitive analysis was achieved after derivatization with 2,4-dinitrophenylhydrazine. LC-MS with atmospheric pressure chemical ionization showed a strong [M-1](-) at m/z 443 for the derivatives. Based on these analytical data, a pheromone extract of a sesiid moth, Macroscelesia japona, was examined by HPLC and LC-MS, and it was confirmed that the octadecadienal tentatively identified by a previous GC-MS analysis did indeed have the 2E,13Z configuration. Furthermore, field evaluation of four synthetic geometric isomers of the 2,13-dienal revealed specific attraction to a lure with the (2E,13Z)-isomer as a main component" |
| Keywords: | "Aldehydes/chemical synthesis/*chemistry Animals Chromatography, Gas Chromatography, High Pressure Liquid Female Isomerism Mass Spectrometry Moths/*metabolism Sex Attractants/chemical synthesis/*chemistry;" |
| Notes: | "MedlineIslam, A Yamamoto, Masanobu Sugie, Mieko Naka, Hideshi Tabata, Jun Arita, Yutaka Ando, Tetsu eng Research Support, Non-U.S. Gov't 2007/07/31 J Chem Ecol. 2007 Sep; 33(9):1763-73. doi: 10.1007/s10886-007-9334-x. Epub 2007 Jul 28" |
