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

Abstract

Abstract1,2,3‐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.

Dimethyl sulfite a potential agent for methylation

“…6 Lemaire group has conducted the formation of ethers from glycerol by phase transfer catalysis, so that 1,2,3-trimethoxypropane was obtained in 95% yield and 96% selectivity in one step with dimethyl sulfate as the methylating agent, potassium hydroxide as the base, in the presence of tetrabutyl ammonium hydrogen sulfate at room temperature. 7 Despite that dimethyl sulfate is available in industry, it is mutagenic showing very high toxicity. 8 The use of methanol provides safer catalytic reactions, but these reactions require a large excess of MeOH as well as high temperatures which ensure the degradation of alcohol leading to the formation of alkene derivatives and dimethyl ether, finally giving moderate selectivities.…”

A novel route to synthesis of glycerol dimethyl ether from epichlorohydrin with high selectivity

“…Highly methylated glycerol ethers including glyceryl dimethyl ethers (GDMEs) and glyceryl trimethyl ether (GTME) were separately as an oxygenate additive, a green solvent or as an anti-freezer, and often produced by the methylation of glycerol with highly toxic dimethyl sulfate [16,17]. However, the results show that the above routes to produce methylated glycerol ethers have the drawbacks of serious side-reaction and poor selectivity.…”

Methylation of Polyols with Trimethylphosphate in the Presence of a Lewis or Brønsted Acid Catalyst

“…[1, 2] Even in light of research into new solvents, [3] hydrotropes, [4] surfactants, [5] or additives for gasolines, [6] the transformation of glyceroland other polyols remains in strong demand. The methodology was also adjusted to carry out peralkylation with longer alkyl chains.…”

“…[1, 2] Even in light of research into new solvents, [3] hydrotropes, [4] surfactants, [5] or additives for gasolines, [6] the transformation of glyceroland other polyols remains in strong demand. [1, 2] Even in light of research into new solvents, [3] hydrotropes, [4] surfactants, [5] or additives for gasolines, [6] the transformation of glyceroland other polyols remains in strong demand.…”

“…The methodology was also adjusted to carry out peralkylation with longer alkyl chains.Interest in oxygenated bio-based molecules has increased with the research into alternatives to petroleum-based products. [1, 2] Even in light of research into new solvents, [3] hydrotropes, [4] surfactants, [5] or additives for gasolines, [6] the transformation of glyceroland other polyols remains in strong demand. Ether derivatives are generally preferred to esters because of their stability,n otably in the presenceo fw ater.I na ddition, ar ecent study dealingw ith the toxicityo fg lycerol ethersh as furtherincreasedi nterest in the selectives ynthesis of such compounds.…”