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Octafluorotoluene as a derivatizing agent for steroids in human plasma
Author(s) -
Baker Michael H.,
Howe Ian,
Jarman Michael,
McCague Raymond
Publication year - 1988
Publication title -
biomedical and environmental mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0887-6134
DOI - 10.1002/bms.1200160138
Subject(s) - derivatization , chemistry , chromatography , reagent , enol , mass spectrometry , organic chemistry , dimethylformamide , mass spectrum , catalysis , solvent
The use of octafluorotoluene (OFT) as a versatile gas chromatographic/mass spectrometric derivatizing agent for steroids containing alcoholic, phenolic or α,β‐unsaturated keto functions, is described. Two distinct derivatizing schemes can be utilized, involving (method 1) a phase‐transfer reaction, employing a two‐phase system of CH 2 Cl 2 and N NaOH with n ‐Bu 4 NHSO 4 as catalyst (suitable for alcoholic and phenolic steroids) and (method 2) a reaction conducted in anhydrous dimethylformamide at 155°C with CsF as base (appropriate for α,β‐unsaturated keto steroids). Perfluorotolyl (PFT) ethers and/or enol ethers have thus been generated. The electron impact spectra display abundant high‐mass molecular ions where derivatization has occurred at a phenolic or enolic function. An extraction, derivatization and gas chromatographic/mass spectrometric scheme has been devised involving method 2 for the analysis of steroids in human plasma. A preliminary quantitative investigation of the levels of testosterone in plasma has been carried out employing these methods. The anomalously high level found is explained in terms of the presence in plasma of lipid‐soluble derivatives of testosterone (probably fatty acid esters) which generate the testosterone bis‐OFT derivative under the reaction conditions employed.