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Eur. J. Mass Spectrom. 10, 1–19 (2004)
DOI: 10.1255/ejms.619

Derivatization in mass spectrometry. 3. Alkylation(arylation)

John M. Halket
Drug Control Centre, King’s College London, Franklin-Wilkins Building, Stamford Street, London SE1 9NN, UK. E-mail: john.halket@kcl.ac.ukVladimir G. Zaikin
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia. E-mail: zaikin@ips.ac.ru

ABSTRACT:
The review is devoted to alkylation (arylation) as a widely employed derivatization procedure for the protection of OH (carboxylic acids, phosphoric acids, sulfonic acids, alcohols, polyols, phenols, enols), SH (thiols) and NH (amines, amides) groups in order to increase volatility, to improve the chromatographic properties and, if possible, mass spectral properties of derivatives. Chemical aspects of derivatization and various alkylation (arylation) reagents and reaction procedures are described. Specific mass spectral (electron ionization, chemical ionization) features of derivatives helpful in identification, structure elucidation, profiling and quantitative determination of the above-mentioned polar compounds by coupled gas chromatography or high-performance liquid chromatography are discussed. Some common analytical applications of the procedures in organic chemistry, clinical chemistry, environmental chemistry etc. are briefly summarized.

Keywords: alcohols, alkylation, alkylating agents, alkyl halides, arylation, diazomethane, derivatives, derivatization, phenols, thiols, amines, amides, carboxylic acids, chemical warfare agents, phosphonic acids, phosphoric acids, sulfonic acids, pentafluorobenzyl derivatives, picolinyl esters, trimethylsilyldiazomethane, electron ionization, chemical ionization, gas chromatography/mass spectrometry, high-performance liquid chromatography/mass spectrometry

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