Nucleophilic Addition of Alcohols: Acetal Formation

It has been demonstrated that water adds rapidly to the carbonyl function of aldehydes and ketones to form geminal-diol. In a similar reaction alcohols add reversibly to aldehydes and ketones to form hemiacetals (hemi, Greek, half). This reaction can continue by adding another alcohol to form an acetal. Hemiacetals and acetals are important functional groups because they appear in sugars.

To achieve effective hemiacetal or acetal formation, two additional features must be implemented. First, an acid catalyst must be used because alcohol is a weak nucleophile; and second, the water produced with the acetal must be removed from the reaction by a process such as a molecular sieves or a Dean-Stark trap. The latter is important, since acetal formation is reversible. Indeed, once pure hemiacetal or acetals are obtained they may be hydrolyzed back to their starting components by treatment with aqueous acid and an excess of water.