One-pot synthesis of ?-valerolactone from tetrahydrofurfuryl alcohol and ?-valerolactone amidation over Сu/ZnO-Al<sub>2</sub>O<sub>3</sub> catalyst

V. V. Brei; A. M. Varvarin; S. V. Prudius

doi:10.15407/hftp07.04.395

Authors

V. V. Brei Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
A. M. Varvarin Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
S. V. Prudius Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine

DOI:

https://doi.org/10.15407/hftp07.04.395

Keywords:

catalytic dehydrogenation, tetrahydrofurfuryl alcohol, δ-valerolactone, δ-valerolactam, Cu-catalyst

Abstract

It has been found that tetrahydrofurfuryl alcohol transforms into ?-valerolactone over Сu/ZnO-Al2O3 catalyst at 270–280°С. ?-Valerolactone can be used for obtaining biodegradable polyesters and copolymers. Proposed Сu/ZnAl-1 catalyst containing 40 wt. % of CuO provides 40–50% alcohol conversion with 80–85% lactone selectivity under hydrogen flow at 0.1 MPa. The reaction pathway from tetrahydrofurfurol to ?-valerolactone has been proposed: it is speculated that alcohol is initially dehydrogenated into tetrahydrofurfural, which rearranges to lactone. Vapor-phase amidation of ?-valerolactone with ammonia into ?-valerolactam, as raw material for obtaining polyamide nylon-5, was also investigated. It has been shown that among studied Cu-containing oxides Сu/ZnAl-1 catalyst provides higher 80 % ?-valerolactam selectivity at 90% lactone conversion at 280°С under ammonia, hydrogen and steam flow with strictly certain molar ratio. The process proceeds via disclosure of lactone cycle with intermediate 5-hydroxypentamide formation.

References

1. Bozell J.J., Petersen G.R. Technology Development for the production of biobased products from biorefinery carbohydrates–the US Department of Energy's «Top 10» revisited. Green Chem. 2010. 12(4): 539. https://doi.org/10.1039/b922014c

2. Corma A., Iborra S., Velty A. Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 2007. 107(6): 2411. https://doi.org/10.1021/cr050989d

3. Mao L., Zhang L., Gao N., Li A. FeCl3 and acetic acid co-catalysed hydrolysis of corncob for improving furfural production and lignin removal from residue. Bioresour. Technol. 2012. 123: 324. https://doi.org/10.1016/j.biortech.2012.07.058

4. Chheda J.N., Huber G.W., Dumesic J.A. Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. Angew. Chem. Int. Edit. 2007. 46(38): 7164. https://doi.org/10.1002/anie.200604274

5. Koso S., Ueda N., Shinmi Y., Okumura K., Kizuka T., Tomishige K. Promoting effect of Mo on the hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Rh/SiO2. J. Catal. 2009. 267(1): 89. https://doi.org/10.1016/j.jcat.2009.07.010

6. Koso S., Furikado I., Shimao A., Miyazawa T., Kunimori K., Tomishige K. Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol. Chem. Commun. 2009. 15: 2035. https://doi.org/10.1039/b822942b

7. Solaro R., Cantoni G., Chiellini E. Polymerisability of different lactones and methyl methacrylate in the presence of various organoaluminium catalysts. Eur. Polym. J. 1997. 33(2): 205. https://doi.org/10.1016/S0014-3057(96)00126-7

8. Lou X., Detrembleur C., Jérome R. Living cationic polymerization of δ-valerolactone and synthesis of high molecular weight homopolymer and asymmetric telechenic and block copolymer. Macromolecules. 2002. 35(4): 1190. https://doi.org/10.1021/ma0113677

9. Darensbourg D.J., Karroonnirum O., Wilson S.J. Ring-opening polymerization of cyclic esters and trimethylene carbonate catalyzed by aluminum half-salen complexes. Inorg. Chem. 2011. 50(14): 6775. https://doi.org/10.1021/ic2008057

10. Yang J., Jia L., Hao Q., Li Y., Li Q., Fang Q., Cao A. New biodegradable amphiphilic block copolymers of ε-caprolactone and δ-valerolactone catalysed by novel aluminum metal complexes. II. Micellization and solution to gel transition. Macromol. Biosci. 2005. 5(9): 896. https://doi.org/10.1002/mabi.200500096

11. Lee H., Zeng F., Dunne M., Allen C. Methoxy poly(ethylene glycol)-block-Poly(δ-valerolactone) copolymer micelles for formulation of hydrophobic drugs. Biomacromolecules. 2005. 6(6): 3119. https://doi.org/10.1021/bm050451h

12. Zeng F., Lee H., Allen C. Epidermal growth factor-conjugated poly(ethylene glycol))-block- poly(δ-valerolactone) copolymer micelles for targeted delivery of chemotherapeutics. Bioconjugate Chem. 2006. 17(2): 399. https://doi.org/10.1021/bc050350g

13. Bagnall W.H., Goodings E.P., Wilson C.I. Reactions of furan compounds. XII. Elimination of the side chain of tetrahydrofurfuryl alcohol using nickel-copper catalysts. J. Am. Chem. Soc. 1951. 73(10): 4794. https://doi.org/10.1021/ja01154a094

14. Thomas H.P., Wilson C.L. Reactions of furan compounds. XV. Behavior of tetrahydrofurfuryl alcohol over iron-copper catalysts. J. Am. Chem. Soc. 1951. 73(10): 4803. https://doi.org/10.1021/ja01154a097

15. Zheng H.-Y., Zhu Y.-L., Teng B.-T., Bai Z.-Q., Zhang C.-H., Xiang H.-W., Li Y.-W. Towards understanding the reaction pathway in vapour phase hydrogenation of furfural to 2-methylfuran. J. Mol. Catal. A: 2006. 246(1): 18. https://doi.org/10.1016/j.molcata.2005.10.003

16. Whelan T. Polymer Technology Dictionary. (London: Chapman & Hall, 1994). https://doi.org/10.1007/978-94-011-1292-5

17. Patent UK 821982 A. Duxbury F.K., Reynolds R.J.W. Manufacture of amides. 1959.

18. Ono Y., Takeyama Y., Hatada K., Keii T. Conversion of δ-valerolactone into 2-piperidone over synthetic zeolites. Ind. Eng. Chem. Prod. Res. Develop. 1976. 15(3): 180. https://doi.org/10.1021/i360059a007

19. Patent FR 1506874(A). Kanegafuchi Boseki Kabushiki Kaisha. Procédé de fabrication d'epsilon-caprolactame. 1967.

20. Patent US 3888845. Fujita Y., Naruchi T., Yoshisato E. Process for producing epsilon-caprolactam. 1975.

21. Inshina E.I., Shistka D.V., Telbiz G.M., Brei V.V. Hammet acidity function for mixed ZrO2-SiO2 oxide at elevated temperatures. Chem. Phys. Technol. Surf. 2012. 3(4): 395.

22. Atake I., Nishida K., Li D., Shishido T., Oumi Y., Sano T., Takehira K. Catalytic behavior of ternary Cu/ZnO/Al2O3 systems prepared by homogeneous precipitation in water-gas shift reaction. J. Mol. Catal. A. 2007. 275(1–2): 130. https://doi.org/10.1016/j.molcata.2007.05.040

23. Sharanda M.E., Prudius S.V., Brei V.V. One-pot synthesis of ethylacetate from ethanol over Cu/ZnO-ZrO2-Al2O3 catalyst. Ukr. Khim. Zh. 2008. 74(12): 78. [in Russian].

24. Sato S., Igarashi J., Yamada Y. Stable vapor-phase conversion of tetrahydrofurfuryl alcohol into 3,4-2H-dihydropyran. Appl. Catal. A. 2013. 453: 213. https://doi.org/10.1016/j.apcata.2012.12.017

25. Gulkova D., Kraus M. Dehydrogenation of substituted alcohols to aldehydes on zinc oxide-chromium catalysts. Collec. Czech. Chem. Commun. 1992. 57: 2215. https://doi.org/10.1135/cccc19922215

26. Nenitescu C.D. Organic Chemistry. V. 2. (Moskow: IIL, 1963). [in Russian].