Abstract
Glycerol has been successfully employed as a versatile and alternative green solvent in variety of organic reactions and synthesis methodologies. Using this valuable green solvent, high product conversions and selectivities were achieved affording innovative solutions to the substitution of the conventionally used volatile organic solvents. Besides solubility of the reactants and the catalysts and easy separation of the products, glycerol offers several other benefits such as catalyst recycling, microwave-assisting reaction, and emulsion mode. This chapter summarizes selected examples of potential uses of glycerol in organic reactions as well as the advantages and disadvantages of such a green methodology.
Furthermore, because of economical and environmental considerations nowadays, the possibility of directly using crude glycerol produced by the biodiesel industry has significantly increased.
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References
Reichardt C (1979) Solvent effects in organic chemistry. Verlag Chemie, Weinheim
Calvino-Casilda V, Guerrero-Pérez MO, Bañares MA (2009) Efficient microwave-promoted acrylonitrile sustainable synthesis from glycerol. Green Chem 11:939–941
Wolfson A, Dlugy C (2007) Palladium-catalyzed Heck and Suzuki coupling in glycerol. Chem Pap 61:228–232
Anastas PT, Warner JC (2000) Green chemistry: theory and practice. Oxford University Press, Oxford
Sheldon RA, Arends I, Hanefeld U (2007) Green chemistry and catalysis. Wiley-VCH, Weinheim
Wolfson A, Dlugy C, Tavor D et al (2006) Baker’s yeast catalyzed asymmetric reduction in glycerol. Tetrahedron Asym 17:2043–2045
Gu Y, Jerome F (2010) Glycerol as a sustainable solvent for green chemistry. Green Chem 12:1127–1138
Wolfson A, Dlugy C, Shotland Y (2007) Glycerol as a green solvent for high product yields and selectivities. Environ Chem Lett 5:67–71
Wolfson A, Dlugy C (2009) Glycerol as an alternative green medium for carbonyl compound reductions. Org Commun 2:34–41
Wolfson A, Haddad N, Dlugy C et al (2008) Baker’s yeast catalyzed asymmetric reduction of methyl acetoacetate in glycerol containing systems. Org Commun 1:9–16
Wolfson A, Tavor D, Dlugy C, Shotland Y (2008) Employing glycerol in transfer hydrogenation-dehydrogenation reactions. US Patent 61/137239
Javor D, Sheviev O, Dlugy C, Wolfson A (2010) Transfer hydrogenations of benzaldehyde using glycerol as solvent and hydrogen source. Canadian J Chem 88:305–308
Wolfson A, Dlugy C, Shotland Y, Tavor D (2009) Glycerol as solvent and hydrogen donor in transfer hydrogenation–dehydrogenation reactions. Tetrahedron Lett 50:5951–5953
Eichner K, Karel M (1972) The influence of water content and water activity on the sugar-amino browning reaction in model systems under various conditions. J Agr Food Chem 20:218–223
Mustapha WAW, Hill SE, Blanshard JMV, Derbyshire W (1998) Maillard reactions: do the properties of liquid matrices matter? Food Chem 62:441–449
Jousse E, Jongen T, Agterof W et al (2002) Simplified kinetic scheme of flavor formation by the Maillard reaction. Food Chem Toxicol 67:2535–2542
Cerny C, Guntz-Dubini R (2006) Role of the solvent glycerol in the Maillard reaction of D-fructose and L-alanine. J Agric Food Chem 54:574–577
Heck RF (1985) Palladium reagents in organic synthesis. Academic, New York
Overman LE, Ricca DJ, Tran VD (1993) First total synthesis of scopadulcic acid B. J Am Chem Soc 115:2042–2044
Link JT, Overman LE (1998) In: Diederich F, Stang PJ (eds) Metal-catalyzed cross-coupling reactions. Wiley-VCH, New York
Haberli A, Leumann CJ (2001) Synthesis of pyrrolidine C-nucleosides via Heck reaction. Org Lett 3:489–492
Stinson SC (1999) Chiral drug interactions. Chem Eng News 77:81–101
Herkes FE (1998) Catalysis of organic reactions. Marcel Dekker, New York; Chapter 33
Alonso F, Beletskaya IP, Yus M (2005) Non-conventional methodologies for transition-metal catalysed carbon–carbon coupling: a critical overview. Part 1: the Heck reaction. Tetrahedron 61:11771–11835
Wolfson A, Litvak G, Dlugy C et al (2009) Employing crude glycerol from biodiesel production as an alternative green reaction medium. Ind Crop Prod 30:78–81
Calvino-Casilda V, Guerrero-Pérez MO, Bañares MA (2010) Microwave-activated direct synthesis of acrylonitrile from glycerol under mild conditions: effect of niobium as dopant of the V-Sb oxide catalytic system. Appl Catal B Environ 95:92–196
Kappe CO (2004) Controlled microwave heating in modern organic synthesis. Angew Chem Int Ed 43:6250–6284
Gu Y, Barrault J, Jerome F (2008) Glycerol as an efficient promoting medium for organic reactions. Adv Synt Catal 350:2007–2012
Li M, Chen C, He F, Gu Y (2010) Multicomponent reactions of 1,3-cyclohexanediones and formaldehyde in glycerol: stabilization of paraformaldehyde in glycerol resulted from using dimedone as substrate. Adv Synth Catal 352:519–530
Lenardao EJ, Trecha DO, Ferreira P da C et al (2009) Green michael addition of thiols to electron deficient alkenes using kf/alumina and recyclable solvent or solvent-free conditions. J Braz Chem Soc 20:93–99
He F, Li P, Gu Y, Li G (2009) Glycerol as a promoting medium for electrophilic activation of aldehydes: catalyst-free synthesis of di(indolyl)methanes, xanthene-1,8(2H)-diones and 1-oxo-hexahydroxanthenes. Green Chem 11:1767–1773
Wolfson A, Atyya A, Dlugy C, Tavor D (2010) Glycerol triacetate as solvent and acyl donor in the production of isoamyl acetate with Candida antarctica lipase B. Bioprocess Biosyst Eng 33:363–366
Andrade LH, Piovan L, Pasquini MD (2009) Improving the enantioselective bioreduction of aromatic ketones mediated by Aspergillus terreus and Rhizopus oryzae: the role of glycerol as a co-solvent. Tetrahedron Asymm 20:1521–1525
Torres S, Castro GR (2004) Non-aqueous biocatalysis in homogeneous solvent systems. Food Technol Biotechnol 42:271–277
Affleck R, Haynes CA, Clark DS (1992) Proc Natl Acad Sci USA 89:5167–5170
Gorman LA, Dordick JS (1992) Organic solvents strip water off enzymes. J Biotechnol Bioeng 39:392–397
Castro GR (1999) Enzymatic activities of proteases dissolved in organic solvents. Enzyme Microb Technol 25:689–694
Bromberg LE, Klibanov AM (1995) Transport of proteins dissolved in organic solvents across biomimetic membranes. Proc Natl Acad Sci USA 92:1262–1266
Rariy RV, Klivanov AM (1999) Protein refolding in predominantly organic media markedly enhanced by common salts. Biotechnol Bioeng 62:704–710
Xu K, Griebenow K, Klibanov AM (1997) Correlation between catalytic activity and secondary structure of subtilisin dissolved in organic solvents. Biotechnol Bioeng 56:485–491
Knubovets T, Osterhout JJ, Connolly PJ, Klibanov AM (1999) Structure, thermostability, and conformational flexibility of hen egg-white lysozyme dissolved in glycerol. Proc Natl Acad Sci USA 96:1262–1267
Knubovets T, Osterhout JJ, Klibanov AM (1999) Structure of lysozyme dissolved in neat organic solvents as assessed by NMR and CD spectroscopies. Biotechnol Bioeng 63:242–248
Castro GR (2000) Properties of soluble α-chymotrypsin in neat glycerol and water. Enzyme Microb Technol 27:143–150
Kramer HA (1940) Brownian motion in a field of force and the diffusion model of chemical reactions. Physica 7:284–304
Jacob M, Schmid FX (1999) Protein folding as a diffusional process. Biochemistry 38:13773–13779
Uribe S, Sampedro JG (2003) Measuring solution viscosity and its effect on enzyme activity. Biol Proced Online 5:108–115
Castro GR, Knubovets T (2003) Homogeneous biocatalysis in organic solvents and water-organic mixtures. Crit Rev Biotechnol 23:195–231
Pace CN (2001) Polar group burial contributes more to protein stability than nonpolar group burial. Biochemistry 40:310–313
Washel A (1998) Electrostatic origin of the catalytic power of enzymes and the role of preorganized active sites. J Biol Chem 273:27035–27038
Torres S, Castro GR (2003) Organic solvent resistant lipase produced by thermoresistant bacteria. In: Roussos S, Soccol CR, Pandey A, Augur C (eds) New horizons in biotechnology. Kluwer Academic Publishers, Dordrecht, pp 113–122
Karam A, Villandier N, Delample M et al (2008) Rational design of sugar-based-surfactant combined catalysts for promoting glycerol as a solvent. Chem Eur J 14:10196–10200
Delample M, Villandier N, Douliez JP, Camy S et al (2010) Glycerol as a cheap, safe and sustainable solvent for the catalytic and regioselective b, b-diarylation of acrylates over palladium nanoparticles. Green Chem 12:804–808
Pouilloux Y, Barrault J, Jerome F (2010) Green Chem 12:804–808
Tan JN, Li M, Gu Y (2010) Multicomponent reactions of 1,3-disubstituted 5-pyrazolones and formaldehyde in environmentally benign solvent systems and their variations with more fundamental substrates. Green Chem 12:908–914
García-Marín H, van der Toorn JC, Mayoral JA et al (2009) Glycerol-based solvents as green reaction media in epoxidations with hydrogen peroxide catalysed by bis[3,5-bis(trifluoromethyl)-diphenyl] diselenide. Green Chem 11:1605–1609
García JI, García-Marín H, Mayoral JC, Pérez P (2010) Synthesis and physico-chemical properties of alkyl glycerol ethers. Green Chem 12:426–434
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V. Calvino-Casilda thanks CSIC for a postdoctoral contract (JAE-Doc).
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Calvino-Casilda, V. (2012). Glycerol as an Alternative Solvent for Organic Reactions. In: Mohammad, A. (eds) Green Solvents I. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-1712-1_6
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DOI: https://doi.org/10.1007/978-94-007-1712-1_6
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