Glycerol carbonate synthesis

Triglycerides are nontoxic, biodegradable and renewable molecules which are being used as substrate for the synthesis of a variety of useful molecules such as glycerol esters, fatty acid alkyl esters, triacetin, ketals, acetals, glycerol carbonates, etc (Scheme 1). 

The glycerolysis of urea represents an alternative synthetic approach for the synthesis of glycerol carbonate (Equation 7.26) ... 

The major problem of the direct carbonatation of alcohols is of course the formation of water and the unfavorable thermodynamics of the process. Attempts to overcome this problem include the addition of water-trapping agents or start from alcohol derivatives such as ortho esters. A number of such experiments have been carried out under conditions considerably beyond the critical data of pure CO2 [88]. The presence of the supercritical phase as a solvent was explicitly addressed in the synthesis of glycerol carbonate from glycerol and CO2 [89]. The tin-catalyzed conversion of trimethyl ortho ester to dimethyl carbonate in SCCO2 occurred with up to ca. 30 catalytic turnovers, whereby the highest yields and selectivities were observed in the vicinity of the critical pressure of pure CO2 [90]. 

P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate in presence of zeolite A... 

Scheme 6.36 Synthesis routes and utilizations of glycerol carbonate.

TGs are composed of a 3 carbon glycerol to which 3 fatty acids are esterified, and the glycerol carbons are stereo-specifically numbered as snl, sn2, and sn3 (Iimis 2011). The mammary gland actively uptakes FAs from plasma for the de novo synthesis of TGs (Neville and Picciano 1997), where, there is a preferential acylation of fatty acids to specific positions in TGs, making it seem as there is a biological purpose for investing in the enzymes needed to achieve the nonrandom positioning of TG fatty acids (Innis 2011). 

Glycerol carbonate (4-hydroxymethyl-2-oxo-l,3-dioxolane) as a versatile building block for tomorrow Synthesis, reactivity, properties and... 

The produced glycerol carbonate has been used as platform molecule for the synthesis of several chemicals, including epichlorohydrin [106]. 

Carrera G, Visak Z, Bogel-Lukasik R, Nunes Da Ponte M (2011) Thermodynamic studies for the synthesis of 1,2-glycerol carbonate from CO2 and glycerol. ICCDU X3, Dijon-FR, September 2011, Book of Abstracts, OC62, p 81... 

Vieville C, Yoo JW, Palet S, Mouloungui Z (1998) Synthesis of glycerol carbonate by direct carbonatation of glycerol in supercritical CO2 in the presence of zeolites and ion exchange resins. Catal Lett 56 245-247... 

Aresta M, Dibenedetto A, Nocito F, Ferragina C (2009) Valorization of bio-glycerol new catalytic materials for the synthesis of glycerol carbonate via glycerolysis of urea J Catal 268 106-114... 

Dibenedetto A, Nocito F, Angelini A, Papai I, Aresta M, Mancuso R (2013) Catalytic synthesis of hydroxymethyl-2-oxazolidinones from glycerol or glycerol carbonate and urea ChemSusChem 6(2) 345-352... 

Scheme 4 Synthesis of glycerol carbonate from epihalohydrins and potassium bicarbonate.

A benzyl carbonate was prepared in 83% yield from the sodium alkoxide of glycerol and benzyl chloroformate (20°, 24 h). It is cleaved by hydrogenolysis (H2/ Pd-C, EtOH, 20°, 2 h, 2 atm, 76% yield) and electrolytic reduction (-2.7 V, R4N X, DMF, 70% yield). A benzyl carbonate was used to protect the hy-droxyl group in lactic acid during a peptide synthesis. 

The interconversion of fructose-6-phosphate and fructose-1,6 bis phosphate is a control point in glycolysis and gluconeogenesis. Gluconeogenesis is a pathway which allows carbon atoms from substrates such as lactate, glycerol and some amino acids to be used for the synthesis of glucose, so it is in effect physiologically the opposite of... 

Prostaglandins are a subgroup of a larger family of compounds known collectively as eicosanoids, which are synthesized from arachidonic acid (arachidonate) this is a 20-carbon omega-6 unsaturated fatty acid (C20 4). The source of the arachidonic acid for PG synthesis is the cell membrane. Most membrane phospholipids have an unsaturated fatty acid as arachidonate at carbon 2 on the glycerol backbone to help maintain membrane fluidity. The arachidonic acid released from the membrane by the... 

Figure 3.15 Hydrogenase synthesis in regulatory mutants of R. eutropha. Cells were grown on agar plates containing glycerol as the carbon source either in the presence or in the absence H2.The cell material was transferred to filter paper and a triphenyl tetra-zolium chloride-based hydrogenase activity staining was performed. Dark colour reflects activity of the MBH.

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