A comparison of t-butyldimethylsilyl and trimethylsilyl ether derivatives for the characterization of urinary metabolites of prostaglandin F2alpha by gas chromatography mass spectrometry.

t-Butyldimethylsilyl and trimethylsilyl ether derivatives of a series of methylated prostaglandin F2alpha metabolites have been compared with respect to their gas chromatographic and mass spectrometric properties. The t-butyldimethylsilyl derivatives had considerably higher retention indices (approximately 2.2 C units per silyl group) than their trimethylsilyl ether counterparts when analysed on the (non-polar) OV-1 stationary phase. Electron impact induced fragmentation patterns were strongly dependent upon the type of silyl ether employed and on the nature of the prostaglandin omega sidechain; the mass spectra of pairs of t-butyldimethylsilyl and trimethylsilyl ether derivatives were found to differ appreciably in several respects and to afford complementatary structural information.