In the present study the potential of solketal transacetalization reaction has been demonstrated as an effective method of synthesis of acetals of glycerol and lipophilic carbonyl compounds (2‐ethylhexanal, n‐decanal, cyclopentanone, cyclohexanone). In solketal transacetalization with 2‐ethylhexanal reaction rate was significantly higher than of direct acetalization of glycerol both with and without a solvent because on the contrary to glycerol solketal is freely miscible with lipophilic compounds. Unlike the direct acetalization, reaction rate increased along with the temperature with no losses in equilibrium conversion. Furthermore, by stripping of by‐product acetone from the reaction zone we have succeeded in increasing the product yield in one‐pot synthesis to 97–98%, so that no further purification is needed. Finally, transacetalization was shown to be catalyzed with solid acids much more efficiently than the direct reaction (the cheap and eco‐friendly montmorillonite K‐10 catalyst was found to be the most active). Based on the regulations revealed, a green atom‐efficient synthetic protocol to obtain higher glycerol acetals and ketals has been proposed.

A synthetic strategy from glycerol to 1,2-propylene glycol (1,2-PG) via heterogeneously catalyzed hydrogenolysis of solketal (2,2-dimethyl-4-(hydroxymethyl)-dioxolane-1,3) has been proposed for the first time. Upon the hydrogenolysis over 60 wt % Cu/Al2O3 at 200–240 °C, solketal has been converted into mixtures of isopropanol and 1,2-PG with high yield (up to 94 mol %). Under similar conditions, the catalyst specific productivity (a yield of 1,2-PG per unit of mass of the catalyst) was about 2.65 times higher, when solketal was the reaction feed instead of glycerol. The reaction was also performed under atmospheric pressure in the vapor phase, where the solketal hydrogenolysis gave 93 mol % selectivity to 1,2-PG with a conversion of 24%. A plausible reaction mechanism for the solketal hydrogenolysis has been proposed.