Cycloorganosilyl derivatives for the determination of alcohols and carboxylic acids by gas chromatography/mass spectrometry

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Eur. J. Mass Spectrom. 5, 23 - 31 (1999)

Cycloorganosilyl derivatives for the determination of alcohols and carboxylic acids by gas chromatography/mass spectrometry

Vladimir G. Zaikin, Vasilii N. Yakushin, El'vira A. Volnina and Anzor I. Mikaya
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia.

ABSTRACT:

New silylating agentsmethyl(trimethylene-, tetramethylene-, pentamethylene)silyl chlorides, ethyl(tetramethylene-, pentamethylene)silyl chlorides and chloromethyl(pentamethylene)silyl chloridesare suggested for the investigation of alcohols and carboxylic acids by gas chromatography/mass spectrometry (GC/MS). It is shown that corresponding derivatives may easily be prepared by solution reactions and by on-column silylation. All the derivatives appeared to be less mobile in GC than trimethylsilyl derivatives. Under electron impact (EI), all the derivatives [except chloromethyl(pentamethylene)silyl derivatives] of primary alcohols form pronounced molecular ions. For all kinds of derivatives obtained from secondary alcohols, the most characteristic fragmentation is due to cleavage of a CC bond near to the silyloxy group. The mass spectra of trimethylene- and tetramethylenesilyl ethers derived from isomeric straight-chain and branched alcohols differ quantitatively. Main fragmentation reactions of the latter derivatives under EI conditions are elucidated with the aid of D-analogues. The mass spectra of cycloorganosilyl esters of alkanoic acids are less characteristic and are due mainly to the loss of an alkyl radical from the silicon atom or to a cleavage of the silacycloalkane ring in molecular ions.

Keywords: Cycloorganosilyl chlorides, derivatization agents, alcohols, carboxylic acids, gas chromatography/mass spectrometry.

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