acetolysis

Acetolysis is the acid-catalyzed cleavage of acetals or acetal-like ethers in the presence of acetic acid. This reaction is typically carried out with a strong Brønsted acid (for example, sulfuric acid or p-toluenesulfonic acid) in glacial acetic acid or an acetic acid–water mixture. The process cleaves the carbon–oxygen bonds of acetals, yielding carbonyl compounds and alcohol fragments. Because the medium contains a high concentration of acetate, the released alcohols or sugar units are often converted to acetyl esters, so the observed products are frequently acetylated derivatives.

Mechanistically, acetolysis proceeds by protonation of the acetal oxygen, formation of a reactive oxocarbenium ion, and attack by acetate or water. The acetate can act as a nucleophile, leading to acetylated products, or subsequent hydrolysis can yield the corresponding carbonyl compound and alcohol. The exact outcome depends on the substrate and the reaction conditions.

Applications of acetolysis are most prominent in carbohydrate chemistry and glycoside analysis. It is used to fragment acetals and glycosidic linkages under conditions that favor formation of acetylated sugar units, facilitating determination of sugar composition, sequence, and linkage patterns in oligosaccharides and polysaccharides. It also serves as a step in preparing acetylated derivatives for analytical characterization or synthetic planning.

Typical conditions involve a solvent system of acetic acid with small amounts of water, catalytic acid, and controlled temperature to balance rate and selectivity. Safety considerations include handling strong acids and corrosive acetic acid under appropriate laboratory protocols.