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Stability of gamma-valerolactone under neutral, acidic, and basic conditions

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Abstract

Dry gamma-valerolactone (GVL) is stable for several weeks at 150 °C and its thermal decomposition only proceeds in the presence of appropriate catalysts. Since GVL does not react with water up to 60 °C for several weeks, it could be used as a green solvent at mild conditions. At higher temperatures, GVL reacts with water to form 4-hydroxyvaleric acid (4-HVA) and reaches the equilibrium in a few days at 100 °C. Aqueous solutions of acids (HCl and H2SO4) catalyze the ring opening of GVL even at room temperature, which leads to the establishment of an equilibrium between GVL, water, and 4-HVA. Although the 4-HVA concentration would be below 4 mol% in the presence of acids, it could be higher than the concentration of a reagent or a catalyst precursor, not to mention a catalytically active species. The latter could be especially worrisome as 4-HVA could be an excellent bi- or even a tri-dentate ligand for transition metals. Aqueous solution of bases (NaOH and NH4OH) also catalyzes the reversible ring opening of GVL. While in the case of NaOH, the product is the sodium salt of 4-hydroxyvalerate, the reversible reaction of GVL, with NH4OH results in the formation of 4-hydroxyvaleric amide. The reversible ring opening of (S)-GVL in the presence of HCl or NaOH has no effect on the stability of the chiral center.

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References

  1. Reichardt C (2007) Solvents and solvent effects: an introduction. Org Process Res Dev 111:105–115

    Article  Google Scholar 

  2. Horváth IT (2008) Solvents from Natute. Green Chem 10:1024–1028

    Article  Google Scholar 

  3. Wypych G (2001) Handbook of solvents. ChemTec Publishing, Toronto

    Google Scholar 

  4. Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press, Oxford

    Google Scholar 

  5. Kerton FM (2009) Alternative solvents for green chemistry. Royal Society of Chemistry, Cambridge

    Google Scholar 

  6. Vigneron JP, Bloy V (1980) Preparation d'alkyl-4 gamma-lactones optiquement actives. Tetrahedron Lett 21:1735–1738

    Article  CAS  Google Scholar 

  7. Mehdi H, Horváth IT, Bodor A (2004) Dehydration and hydrogenation of carbohydrates with aqueous biphase catalysts (CELL 95). 227th ACS National Meeting, Anaheim, CA

    Google Scholar 

  8. Horváth IT (2006) Gamma-valerolactone: a sustainable liquid for energy and carbon based chemicals. The 10th Annual Green Chemistry and Engineering Conference, Washington DC

    Google Scholar 

  9. Mehdi H, Tuba R, Mika LT, Bodor A, Torkos K, Horváth IT (2006) Catalytic conversion of carbohydrates to oxygenates. Renewable resources and renewable energy: a global challenge, Graziani M, Fornasiero P. (Eds), CRC Press: Boca Raton, FL, Chapter 4, 55–60

  10. Horváth IT, Mehdi H, Fábos V, Boda L, Mika LT (2008) γ-valerolactone – a sustainable liquid for energy and carbon-based chemicals. Green Chem 10:238–242

    Article  Google Scholar 

  11. Mehdi H, Fábos V, Tuba R, Bodor A, Mika LT, Horváth IT (2008) Integration of homogeneous and heterogeneous catalytic processes for a multi-step conversion of biomass: from sucrose to levulinic acid, gamma-valerolactone, 1,4-pentanediol, 2-methyl-tetrahydrofuran, and alkanes. Top Catal 48:49–54

    Article  CAS  Google Scholar 

  12. Fábos V, Lui MY, Mui YF, Wong YY, Mika LT, Qi L, Cséfalvay E, Kovács V, Szűcs T, Horváth IT (2015) The use of gamma-valerolactone as an illuminating liquid and lighter fluid. ACS Sus Chem Eng 3:1899–1904

    Article  Google Scholar 

  13. De Bruycker R, Carstensen H-H, Simmie JM, van Geem KM, Marin GB (2015) Experimental and computational study of the initial decomposition of gamma-valerolactone. Proc Combust Inst 35:515–523

    Article  CAS  Google Scholar 

  14. Havasi D, Mizsey P, Mika LT (2016a) Vapor–liquid equilibrium study of the gamma−valerolactone−water binary system. J Chem Eng Data 61:1502–1508

    Article  CAS  Google Scholar 

  15. Havasi D, Pátzay G, Kolarovszki Z, Mika LT (2016b) Isobaric vapor–liquid equilibria for binary mixtures of γ-valerolactone + methanol, ethanol, and 2-propanol. J Chem Eng Data 61:3326–3333

    Article  CAS  Google Scholar 

  16. Fábos V, Koczó G, Mehdi H, Boda L, Horváth IT (2009) Bio-oxygenates and the peroxide number: a safety issue. Energy and Env Sci 2:767–769

    Article  Google Scholar 

  17. Qi L, Horváth IT (2012) Catalytic conversion of fructose to γ-valerolactone in γ-valerolactone. ACS Catal 2:2247–2249

    Article  CAS  Google Scholar 

  18. Bond JQ, Alonso DM, Wang D, West RM, Dumesic JA (2010a) Integrated catalytic conversion of γ-valerolactone to liquid alkenes for transportation fuels. Science 327:1110–1114

    Article  CAS  Google Scholar 

  19. Serrano-Ruiz JC, Wang D, Dumesic JA (2010) Catalytic upgrading of levulinic acid to 5-nonanone. Green Chem 12:574–577

    Article  CAS  Google Scholar 

  20. Bond JQ, Alonso DM, West RM, Dumesic JA (2010b) Valerolactone ring-opening and decarboxylation over SiO2/Al2O3 in the presence of water. Langmuir 26:16291–16298

    Article  CAS  Google Scholar 

  21. Olah GA, Ku AT (1970) Stable carbonium ions. CVIII. Protonated lactones and their cleavage reactions in fluorosulfonic acid-antimony pentafluoride solutions. J Org Chem 35:3916–3922

    Article  CAS  Google Scholar 

  22. Umland J, Witkowski S (1957) Reaction of silver 4-hydroxyvalerate with bromine. J Org Chem 22:345

    Article  CAS  Google Scholar 

  23. Chalid M, Heeres HJ, Broekhuis AA (2012) Ring-opening of γ-valerolactone with amino compounds. J Appl Polym Sci 123:3556–3564

    Article  CAS  Google Scholar 

  24. Fegyverneki D, Orha L, Láng G, Horváth IT (2010) Gamma-valerolactone based solvents. Tetrahedron 66:1078–1081

    Article  CAS  Google Scholar 

  25. Qi L, Mui YF, Lo SW, Lui MY, Akien GR, Horváth IT (2014) Catalytic conversion of fructose, glucose, and sucrose to 5-(hydroxymethyl) furfural and levulinic and formic acids in γ-alerolactone as a green solvent. ACS Sustain Chem Eng 4:1470–1477

    CAS  Google Scholar 

  26. Tukacs JM, Király D, Strádi A, Novodárszki G, Eke Z, Dibó G, Kégl T, Mika LT (2012) Efficient catalytic hydrogenation of levulinic acid: a key step in biomass conversion. Green Chem 14:2057–2065

    Article  CAS  Google Scholar 

  27. Ismalaj E, Strappaveccia G, Ballerini E, Elisei F, Piermatti O, Gelman D, Vaccaro L (2014) γ-Valerolactone as a renewable dipolar aprotic solvent deriving from biomass degradation for the Hiyama reaction. ACS Sustain Chem Eng 2:2461–2464

    Article  CAS  Google Scholar 

  28. Strappaveccia G, Ismalaj E, Petrucci C, Lanari D, Marrocchi A, Drees M, Fachetti A, Vaccaro L (2015a) A biomass-derived safe medium to replace toxic dipolar solvents and access cleaner heck coupling reactions. Green Chem 17:365–372

    Article  CAS  Google Scholar 

  29. Strappaveccia G, Luciani L, Bartollini E, Marrocchi A, Pizzo F, Vaccaro AL (2015b) γ-Valerolactone as an alternative biomass-derived medium for the Sonogashira reaction. Green Chem 17:1071–1076

    Article  CAS  Google Scholar 

  30. Rasina D, Kahler-Quesada A, Ziarelli S, Warratz S, Cao H, Santoro S, Ackermann L, Vaccaro L (2016) Heterogeneous palladium-catalysed Catellani reaction in biomass-derived γ-valerolactone. Green Chem 18:5025–5030

    Article  CAS  Google Scholar 

  31. Horváth IT (2014) Green or sustainable chemistry or both? Chimica Oggi - Chem Today 32:76–79

    Google Scholar 

  32. Tian X, Yang F, Rasina D, Bauer M, Warratz S, Ferlin F, Vaccaro L, Ackermann L (2016) C–H Arylations of 1,2,3-triazoles by reusable heterogeneous palladium catalysts in biomass-derived γ-valerolactone. Chem Commun 52:9777–9780

    Article  CAS  Google Scholar 

  33. Pongrácz P, Kollár L, Mika LT (2016) A step towards hydroformylation under sustainable conditions: platinum-catalysed enantioselective hydroformylation of styrene in gamma-valerolactone. Green Chem 18:842–847

    Article  Google Scholar 

  34. Marosvölgyi-Haskó D, Lengyle B, Tukacs JM, Kollár L, Mika LT (2016) Applicationof γ-valerolactone as an alternative biomass-based medium for aminocarbonylation reactions. Chem Plus Chem. doi:10.1002/cplu.201600389

    Google Scholar 

  35. Gu Y, Jerome F (2013) Bio-based solvents: an emerging generation of fluids for the design of eco-efficient processes in catalysis and organic chemistry. Chem Soc Rev 42:9550–9570

    Article  CAS  Google Scholar 

  36. Soh L, Eckelman MJ (2016) Green solvents in biomass processing. ACS Sustain Chem Eng 4:5821–5837

    Article  CAS  Google Scholar 

  37. Tukacs JM, Fridric B, Dibó G, Székely E, Mika LT (2015) Direct asymmetric reduction of levulinic acid to gamma-valerolactone: synthesis of a chiral platform molecule. Green Chem 17:5189–5195

    Article  CAS  Google Scholar 

  38. http://www1.lsbu.ac.uk/water/water_dissociation.html (accessed on 26/10/2016)

  39. Long FA, Paul MA (1957) Application of the H0 acidity function to kinetics and mechanisms of acid catalysis. Chem Rev 57:935–1010

    Article  CAS  Google Scholar 

  40. Peintler G, (1989–1998) ZiTa, version 5.0; a comprehesive rrogram package for fitting parameters of chemical reaction mechanism; Attila József University: Szeged, Hungary

  41. Bruice TC, Marquardt FH (1962) Hydroxyl group catalysis. IV. The mechanism of intramolecular participation of the aliphatic hydroxyl group in amide hydrolysis. J Amer Chem Soc 84:365–370

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Some of this work was funded by the Innovation and Technology Support Program of the Innovation and Technology Fund of the Government of the Hong Kong SAR (ITS/079/13). Any opinions, findings, conclusions or recommendations expressed in this material (or by members of the project team) do not reflect the views of the Government of the Hong Kong SAR, the Innovation and Technology Commission or the Panel of Assessors for the Innovation and Technology Support Program of the Innovation and Technology Fund. We also thank the Environment and Conservation Fund (ECF/31/2014) for partial financial support. L. T. Mika is grateful for the support of the National Research, Development and Innovation Office—NKFIH, Budapest, Hungary (PD116559), and the János Bolyai Research Scholarship of the Hungarian Academy of Sciences, Budapest, Hungary. A. K. Horváth is grateful for the support of the National Research, Development and Innovation Office, NKFIH, Hungary (K116591).

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Authors and Affiliations

  1. Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong

    Claire Yuet Yan Wong, Alex Wing-Tat Choi, Matthew Y. Lui & István T. Horváth

  2. Department of Chemical and Environmental Process Engineering, Budapest University of Technology and Economics, Műegyetem rkp. 3, Budapest, H-1111, Hungary

    Bálint Fridrich & László T. Mika

  3. Department of Inorganic Chemistry, University of Pécs, Ifjúság útja 6, Pécs, H-7624, Hungary

    Attila K. Horváth

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  1. Claire Yuet Yan Wong
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  2. Alex Wing-Tat Choi
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Correspondence to Attila K. Horváth, László T. Mika or István T. Horváth.

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Dedicated to Professor George A. Olah on the occasion of his 90th birthday.

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Wong, C.Y.Y., Choi, A.WT., Lui, M.Y. et al. Stability of gamma-valerolactone under neutral, acidic, and basic conditions. Struct Chem 28, 423–429 (2017). https://doi.org/10.1007/s11224-016-0887-6

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  • DOI: https://doi.org/10.1007/s11224-016-0887-6

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