Catalytic Synthesis of Hydroxymethyl‐2‐oxazolidinones from Glycerol or Glycerol Carbonate and Urea

Abstract

Oxazolidinones have been synthesized by reacting glycerol carbonate or glycerol with urea in the presence of γ-Zr phosphate as a catalyst. The conversion yield of the polyol or its carbonate depends on the temperature. Below 408 K the selectivity is 100 % with a conversion of up to 25 %, whereas increasing the temperature means that conversion yield grows, but the selectivity decreases, which makes the separation process more difficult. Starting from glycerol carbonate, two isomers, 6 and 6', are formed with a quasi 1:1 molar ratio because urea can attack the carbonate moiety on both sides of the carboxylic CO moiety. From glycerol the formation of the 6' isomer is preferred: the ratio of 6'/6 is close to 7. The oxazolidinones formed act as templates because they interact through hydrogen bonding with glycerol. The intensity of the interaction depends on the 6 or 6' isomer: DFT calculations showed that the energy was 22.6 kcal mol(-1) for 6-oxazolidinone and 25.7 kcal mol(-1) for 6'-oxazolidinone.

New efficient and recyclable catalysts for the synthesis of di- and tri-glycerol carbonates

“…It is used as a component of polyurethane foams, gas separation membranes, surfactants, paints, detergents and as a non-volatile reactive solvent for several types of materials. [47][48][49][50][51][52] Due to its low toxicity, vapor pressure and flammability, good biodegradability and moisturizing ability, glycerol carbonate also possesses the right characteristics of a wetting agent for cosmetic clays or of a carrier for drugs 53,54 Glycerol carbonate is usually prepared by reacting glycerol with toxic phosgene: 55,56 innovative processes such as the direct carboxylation of glycerol with carbon dioxide, 47,57-59 the glycerolysis of urea [60][61][62] or the trans-esterification reaction with linear or cyclic organic carbonates [63][64][65][66] represent ecofriendly alternatives. In recent years, multifunctional monomers based on glycerol carbonate have reached a particular importance in the chemical industry for the production of polyurethanes and polycarbonates (Fig.…”

The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects.

“…In EuroBioref, catalytic technologies were at the core of the project and hereafter some examples of its developments are cited: catalysts were developed for the synthesis of nitriles from fatty acids or esters; for conversion of fatty unsaturated compounds through variations of metathesis reactions . Tandem isomerization/hydroformylation was used for the production of polyamide‐12 precursor from bio‐sourced 10‐undecenenitrile; acetal synthesis was further envisioned through a conventional approach and through reactive distillation or simulated moving bed membrane reactor (SMBR) to overcome chemical equilibriums; glycerol was valorized to various compounds including acrylonitrile, or hydroxymethyl‐ 2 ‐oxazolidinones; glycerol‐derived products were hydroformylated; Guerbet reaction was used to yield various alcohols with applications as aviation fuels; 1 ‐butanol direct conversion to maleic anhydride was developed to be implemented in an original phthalic anhydride ( exo ‐xylene) co‐production configuration; syngas conversion technologies were improved to yield alcohols, as well as methylmercaptan, taking advantage of the presence of H 2 S in black liquor‐derived syngas. In Biocore, chemocatalysis was used to convert C6 cellulose pulp into isosorbide .…”

Direct Assembly of 2‐Oxazolidinones by Chemical Fixation of Carbon Dioxide

“…However, this approach is hitherto hampered by modest selectivities and yields as well as a narrow substrate scope. [9] This affects the costs associated with the industrial production of 2-oxazolidinones significantly enough to restrict their public administration, and trigger research on methods that are simultaneously sustainable and effective, such as those based on the chemical fixation of CO 2 . [5,10] In the last decade, research on the construction of 2-oxazolidinones by chemical fixation of CO 2 has experienced considerable progress.…”