Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species
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Gas chromatography (GC) and mass spectrometry (MS) were used to determine the stereoisomeric compositions of 6,10,14-trimethylpentadecan-2-ol and 6,10,14-trimethylpentadecan-2-one in wing extracts from 17 Bicyclus butterfly species from different regions of Africa. All samples were purified using solid phase extraction (SPE). Since some species contained both alcohol and ketone, these were separated and the ketone was reduced to the alcohol before analysis as either (R)-trans-chrysanthemoyl or (S)-2-acetoxypropionyl esters. A novel asymmetric synthesis was developed for a reference mixture of (2R/S,6S,10R)-6,10,14-trimethylpentadecan-2-ol with known composition of the eight stereoisomers. The mixture then was used as the (R)-trans-chrysanthemoyl esters to correlate each of the eight gas chromatographic peaks to a specific stereoisomer of the extracted wing compounds. Seven butterfly species showed (2R,6R,10R)-configuration of the alcohol, four species contained minute amounts of alcohol too small to determine the stereochemistry, nine species showed (6R,10R)-configuration of the ketone, and one species contained minute amounts of ketone too small to determine the stereochemistry. No other stereoisomers of alcohol or ketone could be detected in the extracts, and the quantities of the compounds in the wing extracts varied from 5 to 900 ng per sample for each species.
KeywordsAsymmetric synthesis GC/MS 6,10,14-Trimethylpentadecan-2-one Wing compounds Stereoisomers
We gratefully acknowledge P. Brakefield and C. Nieberding for financing the collection of wings from the Bicyclus spp butterflies. The research was supported by the EU (European Regional Development Fund) and the County Administrative Board of Västernorrland (Länsstyrelsen).
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