Possible fatty acyl pheromone precursors in Spodoptera littoralis. Search for 11- and 12-hydroxytetradecanoic acids in the pheromone gland.
Lipid extracts of Spodoptera littoralis pheromone glands submitted to acid methanolysis using: (i) sulfuric acid/methanol/benzene (0.1:4:2, by vol) at 90 degrees C for 1 h; (ii) 12 N HCI/methanol (1:2, vol/vol) at 90 degrees C for 1 h, or (iii) 14% BF3-MeOH at 90 degrees C for 1 h did not reveal the presence of either 11- or 12-hydroxytetradecanoic acid in the extracts, as concluded from the gas chromatography-mass spectrometry analyses. Under the above methanolysis conditions, a synthetic sample of methyl (14, 14, 14-2H3) 12-hydroxytetradecanoate remained unaltered. These results may indicate that formation of (E)-11-tetradecenoic acid from tetradecanoic acid does not occur in the pheromone gland by dehydration of an intermediate hydroxyacid. Acid methanolysis of a lipidic extract using BF3-MeOH led to the formation of a mixture of methoxy fatty acid methyl esters, identified by gas chromatography-mass spectrometry. These methoxy derivatives should arise from BF3-catalyzed addition of methanol to the double bond of the natural monounsaturated fatty acyl derivatives present in the gland. Thus, under the same conditions, a synthetic sample of methyl (Z)-11-tetradecenoate was partially transformed into methyl 11-methoxytetradecanoate and methyl 12-methoxytetradecanoate. This reaction might be a useful alternative procedure to obtain methoxy derivatives of olefins, which are very helpful for the structural characterization of the parent alkenes.
Navarro
I
I
Departamento de Química Orgánica Biológica, Centro de Investigación y Desarrollo, Consejo Superior de Investigaciones Científicas, Barcelona, Spain.
Fabriàs
G
G
Camps
F
F
D000818:Animals; D008401:Gas Chromatography-Mass Spectrometry; D006900:Hydroxylation; D009226:Myristates / Q000032:analysis*; D010675:Pheromones / Q000737:chemistry* / Q000378:metabolism; D018411:Spodoptera
C101377:12-hydroxytetradecanoic acid; D009226:Myristates; D010675:Pheromones; C101376:11-hydroxytetradecanoic acid