Mass spectrometry of dimethylthiophosphinates of aromatic hydroxy compounds

Abstract

The mass spectra of 20 differently substituted dimethylthiophosphinic esters of aromatic hydroxy compounds are presented. Fragmentation routes were investigated using high resolution mass measurements, decoupled metastable determinations and deuterium labelling. All compounds exhibited abundant molecular ions and typical phosphorus-containing ions. Characteristic elimination processes strongly dependent upon the respective type of substitution were observed. Due to their high stability, their great ease of formation and their good gas chromatographic properties these new types of derivatives are of special interest for establishing gas chromatography mass spectrometry profiles of acidic catecholamine metabolites.

Thermionic detection in microcolumn liquid chromatography

“…Organic compounds containing hydroxyl and amine functional groups were derivatized to incorporate phosphorus using either , -dimethyl phosphorochloridothioate (Orgmet, Inc., E. Hampstead, NH) (22)(23)(24) or , -diethyl phosphorochloridate (Aldrich) (25). The compounds derivatized in this manner included several hydroxysteroids (Sigma Chemical Co., St. Louis, MO) and aliphatic alcohols (Matheson Coleman & Bell, Norwood, OH).…”

Flame emission detection in microcolumn liquid chromatography

“…The phosphinyl derivatives (20)(21)(22) of deoxycorticosterone, estradiol, cyclohexylamine, and phloroglucinol were obtained through the courtesy of Karl Jacob, Ludwig-Maximilians-Universitat München, West Germany.…”

“…Similarly, molecules containing certain polar functional groups may be derivatized to incorporate phosphorus, and may be subsequently detected with the flame emission detector. Jacob and co-workers (20)(21)(22) have derivatized the less polar hydroxysteroids, amines, and aromatic hydroxy compounds using dimethylthiophosphinyl chloride, followed by gas chromatographic analysis with thermionic detection (alkali flame ionization detector). Since such derivatives were reported to be stable toward hydrolysis, the more polar classes of compounds, which were difficult or impossible to analyze by gas chromatography, might be resolved by using reversed-phase HPLC.…”