Abstract
The synthesis of hydroxenin monoacetate, a key intermediate in the manufacture of vitamin A, relies on the undesirable use of stoichiometric amounts of organic bases such as pyridine. Although the final product (vitamin A acetate) can be produced from hydroxenin diacetate, using the monoacetylated intermediate improves the overall process yield. Aiming to identify more efficient, environmentally benign alternatives, this work first studies the homogeneous acetylation reaction using pyridine. The addition of the base is found to enhance the rate of hydroxenin monoacetate formation, confirming its catalytic role, but also yields non-negligible amounts of hydroxenin diacetate. On the basis of these insights, Mg- and Al-containing hydrotalcites are explored because of their broad scope as base catalysts and the ability to finely tune their properties. The reaction kinetics are greatly enhanced via controlled thermal activation, forming high surface area mixed metal oxides displaying Lewis basic sites. In contrast, a Brønsted basic material synthesized by the reconstruction of a mixed oxide performs similarly to the as-synthesized hydrotalcite. Variation of the Mg/Al ratio from 1 to 3 has no significant impact, but activity losses are observed at higher values because of a reduced number of basic sites. After optimizing the reaction conditions, hydroxenin monoacetate yields >60% are obtained in five consecutive cycles without the need for any intermediate treatment. The findings confirm the potential of hydrotalcite-derived materials as highly selective catalysts for the production of vitamins with reduced levels of organic waste.