Furan

Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen atom. Chemical compounds containing such rings are also referred to as furans.

Furan
Full structural formula of furan
Skeletal formula showing numbering convention
Ball-and-stick model
Space-filling model
Names
Preferred IUPAC name
Furan[1]
Systematic IUPAC name
1,4-Epoxybuta-1,3-diene
1-Oxacyclopenta-2,4-diene
Other names
Oxole
Oxa[5]annulene
1,4-Epoxy-1,3-butadiene
5-Oxacyclopenta-1,3-diene
5-Oxacyclo-1,3-pentadiene
Furfuran
Divinylene oxide
Identifiers
3D model (JSmol)
Beilstein Reference
 103221
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.390
EC Number
  • 203-727-3
Gmelin Reference
 25716
KEGG
RTECS number
  • LT8524000
UNII
UN number 2389
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C4H4O/c1-2-4-5-3-1/h1-4H Y
    Key: YLQBMQCUIZJEEH-UHFFFAOYSA-N Y
  • InChI=1/C4H4O/c1-2-4-5-3-1/h1-4H
    Key: YLQBMQCUIZJEEH-UHFFFAOYAC
SMILES
  • c1ccoc1
Properties
C4H4O
Molar mass 68.075 g·mol−1
Appearance Colorless, volatile liquid
Density 0.936 g/mL
Melting point −85.6 °C (−122.1 °F; 187.6 K)
Boiling point 31.3 °C (88.3 °F; 304.4 K)
-43.09·10−6 cm3/mol
Hazards
GHS labelling:
Pictograms
Signal word
 Danger
Hazard statements
 H224, H302, H315, H332, H341, H350, H373, H412
Precautionary statements
 P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P273, P280, P281, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P308+P313, P312, P314, P321, P330, P332+P313, P362, P370+P378, P403+P235, P405, P501
NFPA 704 (fire diamond)
3
4
1
Flash point −36 °C (−33 °F; 237 K)
Autoignition
temperature
 390 °C (734 °F; 663 K)
Explosive limits Lower: 2.3%
Upper: 14.3% at 20 °C
Lethal dose or concentration (LD, LC):
LD50 (median dose)
 > 2 g/kg (rat)
Safety data sheet (SDS) Pennakem
Related compounds
Related heterocycles
 Pyrrole
Thiophene
Related compounds
 Tetrahydrofuran (THF)
2,5-Dimethylfuran
Benzofuran
Dibenzofuran
Structure
Point group
 C2v
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Furan is a colorless, flammable, highly volatile liquid with a boiling point close to room temperature. It is soluble in common organic solvents, including alcohol, ether, and acetone, and is slightly soluble in water.[2] Its odor is "strong, ethereal; chloroform-like".[3] It is toxic and may be carcinogenic in humans. Furan is used as a starting point for other speciality chemicals.[4]

History

The name "furan" comes from the Latin furfur, which means bran.[5] (Furfural is produced from bran.) The first furan derivative to be described was 2-furoic acid, by Carl Wilhelm Scheele in 1780. Another important derivative, furfural, was reported by Johann Wolfgang Döbereiner in 1831 and characterised nine years later by John Stenhouse. Furan itself was first prepared by Heinrich Limpricht in 1870, although he called it "tetraphenol" (as if it were a four-carbon analog to phenol, C6H5OH).[6][7]

Production

Industrially, furan is manufactured by the palladium-catalyzed decarbonylation of furfural, or by the copper-catalyzed oxidation of 1,3-butadiene:[4]

In the laboratory, furan can be obtained from furfural by oxidation to 2-furoic acid, followed by decarboxylation.[8] It can also be prepared directly by thermal decomposition of pentose-containing materials, and cellulosic solids, especially pine wood.

Synthesis of furans

The Feist–Benary synthesis is a classic way to synthesize furans, although many syntheses have been developed.[9] One of the simplest synthesis methods for furans is the reaction of 1,4-diketones with phosphorus pentoxide (P2O5) in the Paal–Knorr synthesis. The thiophene formation reaction of 1,4-diketones with Lawesson's reagent also forms furans as side products. Many routes exist for the synthesis of substituted furans.[10]

Chemistry

Furan is aromatic because one of the lone pairs of electrons on the oxygen atom is delocalized into the ring, creating a 4n + 2 aromatic system (see Hückel's rule) similar to benzene. Because of the aromaticity, the molecule is flat and lacks discrete double bonds. The other lone pair of electrons of the oxygen atom extends in the plane of the flat ring system. The sp2 hybridization is to allow one of the lone pairs of oxygen to reside in a p orbital and thus allow it to interact within the π system.

Due to its aromaticity, furan's behavior is quite dissimilar to that of the more typical heterocyclic ethers such as tetrahydrofuran.

  • It is considerably more reactive than benzene in electrophilic substitution reactions, due to the electron-donating effects of the oxygen heteroatom. Examination of the resonance contributors shows the increased electron density of the ring, leading to increased rates of electrophilic substitution.[11]
  • Furan serves as a diene in Diels–Alder reactions with electron-deficient dienophiles such as ethyl (E)-3-nitroacrylate.[12] The reaction product is a mixture of isomers with preference for the endo isomer:
Diels-Alder reaction of furan with arynes provides corresponding derivatives of dihydronaphthalenes, which are useful intermediates in synthesis of other polycyclic aromatic compounds.[13]
  • Hydrogenation of furans sequentially affords dihydrofurans and tetrahydrofurans.
  • In the Achmatowicz reaction, furans are converted to dihydropyran compounds.
  • Pyrrole can be prepared industrially by reacting furan and ammonia in the presence of solid acid catalysts, such as SiO2 and Al2O3.[14]

Safety

Furan is found in heat-treated commercial foods and is produced through thermal degradation of natural food constituents.[15][16] It can be found in roasted coffee, instant coffee, and processed baby foods.[16][17][18] Research has indicated that coffee made in espresso makers and coffee made from capsules contain more furan than that made in traditional drip coffee makers, although the levels are still within safe health limits.[19]

Exposure to furan at doses about 2,000 times the projected level of human exposure from foods increases the risk of hepatocellular tumors in rats and mice and bile duct tumors in rats.[20] Furan is therefore listed as a possible human carcinogen.[20]

See also
  • BS 4994 – Furan resin as thermoset FRP for chemical process plant equipments
  • Furanocoumarin
  • Furanoflavonoid
  • Furanose
  • Furantetracarboxylic acid
  • Simple aromatic rings
  • Furan fatty acids
  • Tetrahydrofuran

References
  1. Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 392. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. Jakubke, Hans Dieter; Jeschkeit, Hans (1994). Concise Encyclopedia of Chemistry. Walter de Gruyter. pp. 1–1201. ISBN 0-89925-457-8.
  3. DHHS (NIOSH) Publication No. 2016–171, p. 2, Accessed Nov 2019
  4. Hoydonckx, H. E.; Van Rhijn, W. M.; Van Rhijn, W.; De Vos, D. E.; Jacobs, P. A. "Furfural and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_119.pub2.
  5. Senning, Alexander (2006). Elsevier's Dictionary of Chemoetymology. Elsevier. ISBN 0-444-52239-5.
  6. Limpricht, H. (1870). "Ueber das Tetraphenol C4H4O". Berichte der Deutschen Chemischen Gesellschaft. 3 (1): 90–91. doi:10.1002/cber.18700030129.
  7. Rodd, Ernest Harry (1971). Chemistry of Carbon Compounds: A Modern Comprehensive Treatise. Elsevier.
  8. Wilson, W. C. (1941). "Furan". Organic Syntheses.; Collective Volume, vol. 1, p. 274
  9. Hou, X. L.; Cheung, H. Y.; Hon, T. Y.; Kwan, P. L.; Lo, T. H.; Tong, S. Y.; Wong, H. N. (1998). "Regioselective syntheses of substituted furans". Tetrahedron. 54 (10): 1955–2020. doi:10.1016/S0040-4020(97)10303-9.
  10. Katritzky, Alan R. (2003). "Synthesis of 2,4-disubstituted furans and 4,6-diaryl-substituted 2,3-benzo-1,3a,6a-triazapentalenes" (PDF). Arkivoc. 2004 (2): 109–121. doi:10.3998/ark.5550190.0005.208.
  11. Bruice, Paula Y. (2007). Organic Chemistry (5th ed.). Upper Saddle River, NJ: Pearson Prentice Hall. ISBN 978-0-13-196316-0.
  12. Masesane, I.; Batsanov, A.; Howard, J.; Modal, R.; Steel, P. (2006). "The oxanorbornene approach to 3-hydroxy, 3,4-dihydroxy and 3,4,5-trihydroxy derivatives of 2-aminocyclohexanecarboxylic acid". Beilstein Journal of Organic Chemistry. 2 (9): 9. doi:10.1186/1860-5397-2-9. PMC 1524792. PMID 16674802.
  13. Filatov, M. A.; Baluschev, S.; Ilieva, I. Z.; Enkelmann, V.; Miteva, T.; Landfester, K.; Aleshchenkov, S. E.; Cheprakov, A. V. (2012). "Tetraaryltetraanthra[2,3]porphyrins: Synthesis, Structure, and Optical Properties" (PDF). J. Org. Chem. 77 (24): 11119–11131. doi:10.1021/jo302135q. PMID 23205621. Archived from the original (PDF) on 2020-02-19.
  14. Harreus, Albrecht Ludwig. "Pyrrole". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a22_453.
  15. Anese, M.; Manzocco, L.; Calligaris, S.; Nicoli, M. C. (2013). "Industrially Applicable Strategies for Mitigating Acrylamide, Furan and 5-Hydroxymethylfurfural in Food" (PDF). Journal of Agricultural and Food Chemistry. 61 (43): 10209–14. doi:10.1021/jf305085r. PMID 23627283. Archived from the original (PDF) on 2017-08-08.
  16. Moro, S.; Chipman, J. K.; Wegener, J. W.; Hamberger, C.; Dekant, W.; Mally, A. (2012). "Furan in heat-treated foods: Formation, exposure, toxicity, and aspects of risk assessment" (PDF). Molecular Nutrition & Food Research. 56 (8): 1197–1211. doi:10.1002/mnfr.201200093. hdl:1871/41889. PMID 22641279.
  17. European Food Safety Authority (2011). "Update on furan levels in food from monitoring years 2004–2010 and exposure assessment". EFSA Journal. 9 (9): 2347. doi:10.2903/j.efsa.2011.2347.
  18. Waizenegger, J.; Winkler, G.; Kuballa, T.; Ruge, W.; Kersting, M.; Alexy, U.; Lachenmeier, D. W. (2012). "Analysis and risk assessment of furan in coffee products targeted to adolescents". Food Additives & Contaminants: Part A. 29 (1): 19–28. doi:10.1080/19440049.2011.617012. PMID 22035212. S2CID 29027966.
  19. "Espresso makers: Coffee in capsules contains more furan than the rest". Science Daily. April 14, 2011.
  20. Bakhiya, N.; Appel, K. E. (2010). "Toxicity and carcinogenicity of furan in human diet" (PDF). Archives of Toxicology. 84 (7): 563–578. doi:10.1007/s00204-010-0531-y. PMID 20237914. S2CID 19389984.
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