1,2,3‐Trimethoxypropane and Glycerol Ethers as Bio‐Sourced Solvents from Glycerol. Synthesis by Solvent‐Free Phase‐Transfer Catalysis and Utilization as an Alternative Solvent in Chemical Transformations

1,2,3‐Trimethoxypropane ( 2 ), 1‐alkoxy‐2,3‐dimethoxy‐propanes, and 1‐aryloxy‐2,3‐dimethoxypropanes were prepared in good yields and selectivity by solid–liquid phase‐transfer catalysis in the presence of an inorganic base and an ammonium salt as the phase‐transfer catalyst with no additional solvent. No heating was required, and the synthesis was easily performed under atmospheric pressure on a 150 g scale. For the preparation of 2 , the conversion of glycerol was complete and the selectivity for the expected glycerol trimethylether was above 95 %. This product was utilized as a solvent in organic reactions such as transesterifications between glycerol and vegetable oil, organometallic reactions (Grignard‐ and Barbier‐type reactions), carbon–carbon coupling reactions (Suzuki, Sonogashira, Heck), and in etherification reactions by dehydrogenative alkylation. The solvent showed interesting properties for the solubilization of polymers.