Abstract
Lipidic extracts of Spodoptera littoralis pheromone glands submitted to acid methanolysis using: (i) sulfuric acid/methanol/benzene (0.1∶4∶2, by vol) at 90°C for 1 h; (ii) 12 N HCl/methanol (1∶2; vol/vol) at 90°C for 1 h, or (iii) 14% BF3-MeOH at 90°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, 15-2H3) 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.
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Abbreviations
- FAME:
-
fatty acid methyl esters
- GC-MS:
-
gas-chromatography coupled-mass spectrometry
- 11-MeO-16:Me:
-
methyl 11-methoxyhexadecanoate
- 12-MeO-16:Me:
-
methyl 12-methoxyhexadecanoate
- 9-MeO-14:Me:
-
methyl 9-methoxytetradecanoate
- 10-MeO-14:Me:
-
methyl 10-methoxytetradecanoate
- 11-MeO-14:Me:
-
methyl 11-methoxytetradecanoate
- 12-MeO-14:Me:
-
methyl 12-methoxytetradecanoate
- Z11-14:Me:
-
methyl (Z)-11-tetradecenoate
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Navarro, I., Fabriàs, G. & Camps, F. Possible fatty acyl pheromone precursors in Spodoptera littoralis. Search for 11- and 12-hydroxytetradecanoic acids in the pheromone gland. Lipids 32, 407–412 (1997). https://doi.org/10.1007/s11745-997-0052-x
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DOI: https://doi.org/10.1007/s11745-997-0052-x