Furfuryl alcohol is an organic compound containing a furan substituted with a hydroxymethyl group. It is a colorless liquid, but aged samples appear amber. It possesses a faint odor of burning and a bitter taste. It is miscible with but unstable in water. It is soluble in common organic solvents.[4]
Furfuryl alcohol is manufactured industrially by hydrogenation of furfural, which is itself typically produced from waste bio-mass such as corncobs or sugar canebagasse. As such furfuryl alcohol may be considered a green chemical.[5] One-pot systems have been investigated to produce furfuryl alcohol directly from xylose using solid acid catalysts.[6]
Reactionsedit
It undergoes many reactions including Diels–Alder additions to electrophilic alkenes and alkynes. Hydroxymethylation gives 1,5-bis(hydroxymethyl)furan. Hydrolysis gives levulinic acid. Upon treatment with acids, heat and/or catalysts, furfuryl alcohol can be made to polymerize into a resin, poly(furfuryl alcohol). Hydrogenation of furfuryl alcohol can proceed to give hydroxymethyl derivative of tetrahydrofuran and 1,5-pentanediol. The etherification reaction of furfuryl alcohol with alkyl or aryl halide (e.g. benzyl chloride) in the liquid-liquid-liquid triphase system with the help of a phase transfer catalyst also reported.[7] In the Achmatowicz reaction, also known as the Achmatowicz rearrangement, furfuryl alcohol is converted to a dihydropyran.
Applicationsedit
Resins, compositesedit
The primary use of furfuryl alcohol is as a monomer for the synthesis of furan resins.[4][8] These polymers are used in thermoset polymer matrix composites, cements, adhesives, coatings and casting/foundry resins. Polymerization involves an acid-catalyzed polycondensation, usually giving a black cross-linked product.[9] A highly simplified representation is shown below.
Because of its low molecular weight, furfuryl alcohol can impregnate the cells of wood, where it can be polymerized and bonded with the wood by heat, radiation, and/or catalysts or additional reactants. The treated wood (e.g. "Kebony") has improved moisture-dimensional stability, hardness, and decay and insect resistance; catalysts can include zinc chloride, citric, and formic acid, as well as borates.[10][11]
Use as rocket propellant (fuel component)edit
Furfuryl alcohol has been used in rocketry as a fuel which ignites hypergolically (immediately and energetically in contact) with white fuming nitric acid or red fuming nitric acid oxidizer.[12] The use of hypergolics avoids the need for an igniter. In late 2012, Spectra, a concept liquid rocket engine using white fuming nitric acid as the oxidizer to furfuryl alcohol fuel was static tested by Copenhagen Suborbitals.[13][14]
^Mariscal, R.; Maireles-Torres, P.; Ojeda, M.; et al. (2016). "Furfural: a Renewable and Versatile Platform Molecule for the Synthesis of Chemicals and Fuels" (PDF). Energy Environ. Sci. 9 (4): 1144–1189. doi:10.1039/C5EE02666K. hdl:10261/184700. ISSN 1754-5692. S2CID 101343477.
^Gómez Millán, Gerardo; Sixta, Herbert (23 September 2020). "Towards the Green Synthesis of Furfuryl Alcohol in a One-Pot System from Xylose: a Review". Catalysts. 10 (10): 1101. doi:10.3390/catal10101101.
^Katole DO, Yadav GD. Process intensification and waste minimization using liquid-liquid-liquid triphase transfer catalysis for the synthesis of 2-((benzyloxy)methyl)furan. Molecular Catalysis 2019;466:112–21. https://doi.org/10.1016/j.mcat.2019.01.004
^Brydson, J. A. (1999). "Furan Resins". In J. A. Brydson (ed.). Plastics Materials (Seventh ed.). Oxford: Butterworth-Heinemann. pp. 810–813. doi:10.1016/B978-075064132-6/50069-3. ISBN9780750641326.
^Choura, Mekki; Belgacem, Naceur M.; Gandini, Alessandro (January 1996). "Acid-Catalyzed Polycondensation of Furfuryl Alcohol: Mechanisms of Chromophore Formation and Cross-Linking". Macromolecules. 29 (11): 3839–3850. Bibcode:1996MaMol..29.3839C. doi:10.1021/ma951522f.
^Alfred J., Stamm (1977). "Chapter 9". Wood Technology: Chemical Aspects. ACS Symposium Series. Vol. 43. Washington: American Chemical Society. pp. 141–149. doi:10.1021/bk-1977-0043.ch009. ISBN9780841203730.
^Baysal, Ergun; Ozaki, S.Kiyoka; Yalinkilic, MustafaKemal (21 August 2004). "Dimensional stabilization of wood treated with furfuryl alcohol catalysed by borates". Wood Science and Technology. doi:10.1007/s00226-004-0248-2. S2CID 33699990.
^MUNJAL, N. L. (May 1970). "Ignition catalysts for furfuryl alcohol - Red fuming nitric acid bipropellant". AIAA Journal. 8 (5): 980–981. Bibcode:1970AIAAJ...8..980M. doi:10.2514/3.5816.
^Madsen, Peter. (in Danish). Archived from the original on September 12, 2012. Retrieved September 10, 2012.
^Madsen, Peter. (PDF). Copenhagen Suborbitals. Archived from the original (PDF) on 2013-03-17. Retrieved 2013-05-01.
Literature: K.J. Zeitsch,The Chemistry and Technology of Furfural and its Many By-Products, Elsevier, 2000
January 01, 1970
furfuryl, alcohol, organic, compound, containing, furan, substituted, with, hydroxymethyl, group, colorless, liquid, aged, samples, appear, amber, possesses, faint, odor, burning, bitter, taste, miscible, with, unstable, water, soluble, common, organic, solven. Furfuryl alcohol is an organic compound containing a furan substituted with a hydroxymethyl group It is a colorless liquid but aged samples appear amber It possesses a faint odor of burning and a bitter taste It is miscible with but unstable in water It is soluble in common organic solvents 4 Furfuryl alcohol 1 Names Preferred IUPAC name Furan 2 yl methanol Other names Furan 2 ylmethanolFurfuryl alcohol 2 Furanmethanol2 Furancarbinol2 Hydroxymethyl furan Identifiers CAS Number 98 00 0 Y 3D model JSmol Interactive image ChEBI CHEBI 207496 Y ChEMBL ChEMBL308187 Y ChemSpider 7083 Y ECHA InfoCard 100 002 388 PubChem CID 7361 UNII D582054MUH Y CompTox Dashboard EPA DTXSID2025347 InChI InChI 1S C5H6O2 c6 4 5 2 1 3 7 5 h1 3 6H 4H2 YKey XPFVYQJUAUNWIW UHFFFAOYSA N YInChI 1 C5H6O2 c6 4 5 2 1 3 7 5 h1 3 6H 4H2Key XPFVYQJUAUNWIW UHFFFAOYAV SMILES c1cc oc1 CO Properties Chemical formula C5H6O2 Molar mass 98 10 g mol Appearance colorless liquid Odor burning odor 2 Density 1 128 g cm3 Melting point 29 C 20 F 244 K Boiling point 170 C 338 F 443 K Solubility in water miscible Hazards NFPA 704 fire diamond 321 Flash point 65 C 149 F 338 K 2 Explosive limits 1 8 16 3 2 Lethal dose or concentration LD LC LC50 median concentration 397 ppm mouse 6 hr 85 ppm rat 6 hr 592 ppm rat 1 hr 3 LCLo lowest published 597 ppm mouse 6 hr 3 NIOSH US health exposure limits PEL Permissible TWA 50 ppm 200 mg m3 2 REL Recommended TWA 10 ppm 40 mg m3 ST 15 ppm 60 mg m3 skin 2 IDLH Immediate danger 75 ppm 2 Safety data sheet SDS External MSDS Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Contents 1 Synthesis 2 Reactions 3 Applications 3 1 Resins composites 3 2 Use as rocket propellant fuel component 4 Safety 5 See also 6 References 7 External linksSynthesis editFurfuryl alcohol is manufactured industrially by hydrogenation of furfural which is itself typically produced from waste bio mass such as corncobs or sugar cane bagasse As such furfuryl alcohol may be considered a green chemical 5 One pot systems have been investigated to produce furfuryl alcohol directly from xylose using solid acid catalysts 6 Reactions editIt undergoes many reactions including Diels Alder additions to electrophilic alkenes and alkynes Hydroxymethylation gives 1 5 bis hydroxymethyl furan Hydrolysis gives levulinic acid Upon treatment with acids heat and or catalysts furfuryl alcohol can be made to polymerize into a resin poly furfuryl alcohol Hydrogenation of furfuryl alcohol can proceed to give hydroxymethyl derivative of tetrahydrofuran and 1 5 pentanediol The etherification reaction of furfuryl alcohol with alkyl or aryl halide e g benzyl chloride in the liquid liquid liquid triphase system with the help of a phase transfer catalyst also reported 7 In the Achmatowicz reaction also known as the Achmatowicz rearrangement furfuryl alcohol is converted to a dihydropyran Applications editResins composites edit The primary use of furfuryl alcohol is as a monomer for the synthesis of furan resins 4 8 These polymers are used in thermoset polymer matrix composites cements adhesives coatings and casting foundry resins Polymerization involves an acid catalyzed polycondensation usually giving a black cross linked product 9 A highly simplified representation is shown below nbsp Because of its low molecular weight furfuryl alcohol can impregnate the cells of wood where it can be polymerized and bonded with the wood by heat radiation and or catalysts or additional reactants The treated wood e g Kebony has improved moisture dimensional stability hardness and decay and insect resistance catalysts can include zinc chloride citric and formic acid as well as borates 10 11 Use as rocket propellant fuel component edit Furfuryl alcohol has been used in rocketry as a fuel which ignites hypergolically immediately and energetically in contact with white fuming nitric acid or red fuming nitric acid oxidizer 12 The use of hypergolics avoids the need for an igniter In late 2012 Spectra a concept liquid rocket engine using white fuming nitric acid as the oxidizer to furfuryl alcohol fuel was static tested by Copenhagen Suborbitals 13 14 Safety editThe median lethal dose for furfuryl alcohol ranges from 160 to 400 mg kg mouse or rabbit oral citation needed See also editFurfurylamine corresponding amine 2 Furonitrile corresponding nitrile Furan 2 ylmethanethiol corresponding thiol 2 Furoic acid corresponding carboxylic acidReferences edit Merck Index 11th Edition 4215 a b c d e f NIOSH Pocket Guide to Chemical Hazards 0298 National Institute for Occupational Safety and Health NIOSH a b Furfuryl alcohol Immediately Dangerous to Life or Health Concentrations IDLH National Institute for Occupational Safety and Health NIOSH a b Hoydonckx H E Van Rhijn W M Van Rhijn W et al Furfural and Derivatives Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a12 119 pub2 ISBN 978 3527306732 Mariscal R Maireles Torres P Ojeda M et al 2016 Furfural a Renewable and Versatile Platform Molecule for the Synthesis of Chemicals and Fuels PDF Energy Environ Sci 9 4 1144 1189 doi 10 1039 C5EE02666K hdl 10261 184700 ISSN 1754 5692 S2CID 101343477 Gomez Millan Gerardo Sixta Herbert 23 September 2020 Towards the Green Synthesis of Furfuryl Alcohol in a One Pot System from Xylose a Review Catalysts 10 10 1101 doi 10 3390 catal10101101 Katole DO Yadav GD Process intensification and waste minimization using liquid liquid liquid triphase transfer catalysis for the synthesis of 2 benzyloxy methyl furan Molecular Catalysis 2019 466 112 21 https doi org 10 1016 j mcat 2019 01 004 Brydson J A 1999 Furan Resins In J A Brydson ed Plastics Materials Seventh ed Oxford Butterworth Heinemann pp 810 813 doi 10 1016 B978 075064132 6 50069 3 ISBN 9780750641326 Choura Mekki Belgacem Naceur M Gandini Alessandro January 1996 Acid Catalyzed Polycondensation of Furfuryl Alcohol Mechanisms of Chromophore Formation and Cross Linking Macromolecules 29 11 3839 3850 Bibcode 1996MaMol 29 3839C doi 10 1021 ma951522f Alfred J Stamm 1977 Chapter 9 Wood Technology Chemical Aspects ACS Symposium Series Vol 43 Washington American Chemical Society pp 141 149 doi 10 1021 bk 1977 0043 ch009 ISBN 9780841203730 Baysal Ergun Ozaki S Kiyoka Yalinkilic MustafaKemal 21 August 2004 Dimensional stabilization of wood treated with furfuryl alcohol catalysed by borates Wood Science and Technology doi 10 1007 s00226 004 0248 2 S2CID 33699990 MUNJAL N L May 1970 Ignition catalysts for furfuryl alcohol Red fuming nitric acid bipropellant AIAA Journal 8 5 980 981 Bibcode 1970AIAAJ 8 980M doi 10 2514 3 5816 Madsen Peter Spectra testen in Danish Archived from the original on September 12 2012 Retrieved September 10 2012 Madsen Peter Project SPECTRA Experimental evaluation of a liquid storable propellant PDF Copenhagen Suborbitals Archived from the original PDF on 2013 03 17 Retrieved 2013 05 01 External links editHealth hazards Archived 2021 04 27 at the Wayback Machine CDC NIOSH Pocket Guide to Chemical Hazards Literature K J Zeitsch The Chemistry and Technology of Furfural and its Many By Products Elsevier 2000 Retrieved from https en wikipedia org w index php title Furfuryl alcohol amp oldid 1179904411, wikipedia, wiki, book, books, library,
