On the interactions of alkyl 2-hydroxycarboxylic acids with alkoxysilanes: selective esterification of simple 2-hydroxycarboxylic acids

The interactions of a range of monocarboxylic acids with tetramethoxysilane Si(OMe)(4) (TMOS), in methanol (MeOH), have been investigated by using (1)H, (13)C and (29)Si solution-phase NMR spectroscopy and electrospray mass spectrometry (ESMS). Si(OMe)(4) acts as a catalyst/reagent in the selective methylation of 2-hydroxycarboxylic acids (2HOAs) in MeOH at room temperature: glycolic acid, lactic acid and 2-hydroxybutyric acid are esterified more than a hundred times faster in MeOH and Si(OMe)(4) than in MeOH alone. No acceleration of methylation is observed for carboxylic acids lacking the 2-hydroxy group. Methylation of the 2HOAs is associated with the condensation of individual siloxane units to form oligomers. A mechanism is proposed in which 2HOAs attach to silicon via the alkoxy group, then subsequently via the carboxyl group in an intramolecular rearrangement to form an unstable and reactive cyclic intermediate. This intermediate may lead to accelerated methylation of the carboxylic acid via nucleophilic attack of MeOH at the carbonyl group, while a separate reaction pathway leads to condensation of silanols and/or alkoxysilanes leading to oligosiloxanes. The mechanism has implications for the use of 2HOAs as templates in sol-gel silica preparation.