Reaction of Glycerol with Trimethyl Orthoformate: Towards the Synthesis of New Glycerol Derivatives

The reactivity of glycerol with trimethyl orthoformate is here described with an emphasis on developing a reliable synthetic approach for glycerol valorization. The glycerol based orthoester 4-(dimethoxymethoxy)methyl)-2-methoxy-1,3-dioxolane (3) was synthesized, under catalytic as well as catalyst-free conditions, by taking advantage of the thermodynamically controlled equilibrium between intermediates. Both Brønsted and Lewis acid catalysts accelerated the attainment of such an equilibrium, particularly Brønsted acidic ionic liquids BSMImHSO4 and BSMImBr were the most effective compounds for this reaction. The kinetic profiles allowed the proposal of a mechanism that accounts for the selectivity of the reaction.

Synthesis of allyl alcohol as a method to valorise glycerol from the biodiesel production

The conversion of triglycerides to biodiesel and glycerol to allyl alcohol is described using trimethyl orthoformate.

Pd/C as an efficient heterogeneous catalyst for carbonylative four-component synthesis of 4(3H)-quinazolinones

A relatively mild, operationally simple, phosphine-free and recyclable catalytic system for the carbonylative synthesis of 4(3H)-quinazolinones with 2-iodoanilines, trimethyl orthoformate, and amines as the substrates has been developed.

A facile access to substituted benzo[a]fluorenes from o-alkynylbenzaldehydes via in situ formed acetals

Brønsted acid catalysed reaction of o-alkynylbenzaldehydes with arylalkynes in the presence of trimethyl orthoformate takes a different reaction pathway and results in benzo[a]fluorenes.