Chapter 15 – Phenolic aralkylamines, monohydric alcohols, monocarbaldehydes, monoketones and monocarboxylic acids*

Publisher Summary This chapter discusses the methods of preparation, properties, and reactions of phenolic aralkylamines, monohydric alcohols, monocarbaldehydes, monoketones, and monocarboxylic acids. Synthetic aspects of amidoalkylation are investigated. Hydrolysis of the resulting amides provides a simple route to ring-substituted benzylamines. The reaction of resorcinol with N-(hydroxymethyl)caprolactam occurs readily in acid. Catecholamines and phenethylamines are readily separated as their propionyl derivatives by gas liquid chromatography, using either an OV-101 or an OV-17 silicone stationary phase, high-performance liquid chromatography is effective for the separations of isomeric Cactaceae alkaloids. α-Hydroxyalkylation of phenols occurs exclusively at the ortho-position when phenols are treated with either aliphatic aldehydes, including formaldehyde, or aromatic aldehydes, in the presence of benzene boronic acid. The kinetics of hydroxymethylation is discussed. The rate of hydroxymethylation of hydroquinone, catechol, and resorcinol by protonated formaldehyde in the pH range 0.20–3.30 is enhanced by protonation of one phenolic hydroxyl group. Protonation of a second hydroxyl group has no further effect.