Levulinic acid

Levulinic acid[1]
Names
Preferred IUPAC name
4-Oxopentanoic acid
Other names
Levulinic acid, β-Acetylpropionic acid, 3-Acetopropionic acid, β-acetylpropionic acid, γ-ketovaleric acid
Identifiers
CAS Number
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.004.228
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PubChem CID
UNII
InChI
  • InChI=1S/C5H8O3/c1-4(6)2-3-5(7)8/h2-3H2,1H3,(H,7,8) checkY
    Key: JOOXCMJARBKPKM-UHFFFAOYSA-N checkY
  • InChI=1/C5H8O3/c1-4(6)2-3-5(7)8/h2-3H2,1H3,(H,7,8)
    Key: JOOXCMJARBKPKM-UHFFFAOYAR
SMILES
  • CC(=O)CCC(=O)O
Properties
Chemical formula
 C5H8O3
Molar mass 116.11 g/mol
Density 1.1447 g/cm3
Melting point 33 to 35 °C (91 to 95 °F; 306 to 308 K)
Boiling point 245 to 246 °C (473 to 475 °F; 518 to 519 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Levulinic acid, or 4-oxopentanoic acid, is an organic compound with the formula CH3C(O)CH2CH2CO2H. It is classified as a keto acid. This white crystalline solid is soluble in water and polar organic solvents. It is derived from degradation of cellulose and is a potential precursor to biofuels,[2] such as ethyl levulinate.[3]


Synthesis

Levulinic acid was first prepared by Dutch chemist Gerardus Johannes Mulder by heating fructose with hydrochloric acid. mentioned l.[4] Levulinic acid has nonetheless not reached a commercial use in significant volume.

The first commercial production of levulinic acid began as a batchwise process in an autoclave by starch manufacturer A.E. Staley in the 1940s.[5] In 1953 Quaker Oats developed a continuous process for the production of levulinic acid.[6] In 1956 it was identified as a platform chemical with high potential.[7] and in 2004 the US Department of Energy (U.S. DoE) identified levulinic acid as one of the 12 potential platform chemicals in the biorefinery concept.[8]

The synthesis of levulinic acid from hexoses (glucose, fructose) or starch in dilute hydrochloric acid or sulfuric acid.[4][9][10][11] In addition to formic acid further, partly insoluble, by-products are produced. These are deeply colored and their complete removal is a challenge for most technologies.

Many concepts for the commercial production of levulinic acid are based on a strong acid technology. The processes are conducted in a continuous manner at high pressures and temperatures. Lignocellulose is an inexpensive starting material. Levulinic acid is separated from the mineral acid catalyst by extraction. Levulinic acid is purified by distillation.[12] DSM,[13] Segetis,[14] and GFBiochemicals. GFBiochemicals started the commercial production of levulinic acid in 2015 at a production scale of 2,000 MT/a in Caserta, Italy.[15][16]

Reactions and applications

Levulinic acid is used as a precursor for pharmaceuticals, plasticizers, and various other additives.[17] The largest application of levulinic acid is its use in the production of aminolevulinic acid, a biodegradable herbicide used in South Asia. Another key application is the use of levulinic acid in cosmetics. Ethyl levulinate, a primary derivative of levulinic acid, is extensively used in fragrances and perfumes. Levulinic acid is a chemical building block or starting material for a wide variety of other compounds[18] including γ-valerolactone and 2-methyl-THF.[8]

Other occurrence and niche uses

Levulinic acid is used in cigarettes to increase nicotine delivery in smoke and binding of nicotine to neural receptors.[19]

Etymology

The former term “levulose” for fructose gave levulinic acid its name.

Safety

Levulinic acid is relatively nontoxic, with an LD50 of 1850 mg/kg.[17]

References

  1. ↑ The Merck Index, 15th Ed. (2013), p. 1018, Monograph 5526, O'Neil: The Royal Society of Chemistry. Available online at: http://www.rsc.org/Merck-Index/monograph/mono1500005526
  2. ↑ Biorefineries – Industrial Processes and Products. Status Quo and Future Directions. Vol. 1, Edited by Birgit Kamm, Patrick R. Gruber, Michael Kamm. 2006, WILEY-VCH, Weinheim. ISBN 3-527-31027-4
  3. ↑ Leal Silva, Jean Felipe; Grekin, Rebecca; Mariano, Adriano Pinto; Maciel Filho, Rubens (2018). "Making Levulinic Acid and Ethyl Levulinate Economically Viable: A Worldwide Technoeconomic and Environmental Assessment of Possible Routes". Energy Technology. 6 (4): 613–639. doi:10.1002/ente.201700594. ISSN 2194-4296.
  4. 1 2 Mulder, G. J. (1840). "Untersuchungen über die Humussubstanzen" [Investigations on humic substances]. J. Prakt. Chem. (in German). 21 (1): 203–240. doi:10.1002/prac.18400210121.
  5. ↑ A. E. Staley, Mfg. Co. (Decatur, Ill.); Levulinic Acid 1942 [C.A. 36, 1612]
  6. ↑ US-2813900 (1953)
  7. ↑ R. H. Leonard, Ind. Eng. Chem. 1331, (1956).
  8. 1 2 "Top Value Added Chemicals from Biomass: Volume I--Results of Screening for Potential Candidates from Sugars and Synthesis Gas" (PDF).
  9. ↑ A. Freiherrn, V. Grote, B. Tollens, "Untersuchungen über Kohlenhydrate. I. Ueber die bei Einwirkung von Schwefelsäure auf Zucker entstehende Säure (Levulinsäure)" Justus Liebigs Annalen der Chemie volume 175, pp. 181-204 (1875). doi: 10.1002/jlac.18751750113
  10. ↑ B. F. McKenzie (1941). "Levulinic acid". Organic Syntheses.; Collective Volume, vol. 1, p. 335
  11. ↑ S.L. Suib, New and Future Developments in Catalysis – Catalytic Biomass Conversion, Elsevier, (2013). ISBN 978-0-444-53878-9
  12. ↑ US-5608105
  13. ↑ WO-2014087016 A1
  14. ↑ US-20140128634
  15. ↑ "Commercial-scale production for bio-based levulinic acid - Chemical Engineering | Page 1".
  16. ↑ "GFBiochemicals reaches commercial-scale in renewable levulinic acid project : Biofuels Digest".
  17. 1 2 Franz Dietrich Klingler, Wolfgang Ebertz "Oxocarboxylic Acids" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a18_313
  18. ↑ Bozell, Joseph J.; Petersen, Gene R. (2010-04-06). "Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy's "Top 10" revisited". Green Chemistry. 12 (4): 539–554. doi:10.1039/b922014c.
  19. ↑ Doris Cullen et al., A Guide to Deciphering the Internal Codes Used by the Tobacco Industry, Report No. 03-05, Harvard School of Public Health, Division of Public Health Practice, Tobacco Research Program, August 2005, http://legacy.library.ucsf.edu/resources/harvard_monograph.pdf
  • Dunstan, Wyndham Rowland (1911). "Rubber" . In Chisholm, Hugh (ed.). Encyclopædia Britannica. Vol. 23 (11th ed.). Cambridge University Press. p. 802.
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