Abstract
A catalytic system, including trifluoroacetic acid and organic solvent additives, was applied to carry out the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam. High conversion (100 %) and high selectivity to caprolactam (>99 %) have been successfully obtained using acetonitrile as the additive. The effect of several organic solvents on the reaction was investigated, and the catalyst composition was optimized. The results indicate that the catalytic system with 10 wt% of acetonitrile can give the fastest reaction rate. An immiscible two-phase system was proposed to study the side reaction of oxime hydrolysis which determines the selectivity. Based on the results, a simplified reaction process was suggested and a mathematical kinetic model was developed. The performance of the catalytic system is much better than the classic process. Neutralization agent and ammonium sulfate by-product are both completely avoided.
Graphical Abstract
![](http://media.springernature.com/lw685/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Figa_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Sch1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Fig1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Fig2_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Sch2_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10562-013-1114-3/MediaObjects/10562_2013_1114_Fig3_HTML.gif)
Similar content being viewed by others
References
Beckmann E (1886) Chem Ber 19:988
Zuidhof KT, de Croon MHJM, Schouten JC (2010) AIChE J 56:1297
Zuidhof KT, de Croon MHJM, Schouten JC, Tinge JT (2012) Chem Eng Technol 35:1
Ritz J, Fuchs H, Kieczka H, Moran WC (2001) Ullmann’s encyclopedia of industrial chemistry, 6th edn, Weinheim
Dahlhoff G, Niederer JPM, Hoelderich WF (2001) Cat Rev Sci Eng 43:381
Heitmann GP, Dahlhoff G, Hölderich WF (1999) J Catal 186:12
Fernández AB, Boronat M, Blasco T, Corna A (2005) Angew Chem Int Ed 44:2370
Mao DS, Lu GZ, Chen QL, **e ZK, Zhang YX (2001) Catal Lett 244:273
Bordoloi A, Halligudi SB (2010) Appl Catal A 379:141
Marthala VRR, Frey J, Hunger M (2010) Catal Lett 135:91
Pavel CC, Palkovits R, Schüth F, Schmidt W (2008) J Catal 254:84
Anilkumar M, Hoelderich WF (2012) Catal Today 198:289
Sato O, Ikushima Y, Yokoyama T (1998) J Org Chem 63:9100
Ikushima Y, Hatakeda K, Sato O, Yokoyama T, Arai M (2000) J Am Chem Soc 122:1908
Guo S, Du ZY, Zhang SG, Li DM, Li ZP, Deng YQ (2006) Green Chem 8:296
Zicmanis A, Katkevica S, Mekss P (2009) Catal Commun 10:614
Maia A, Albanese DCM, Landini D (2012) Tetrahedron 68:1947
Yamabe S, Tsuchida N, Yamazaki S (2005) J Org Chem 70:10638
Ronchin L, Bortoluzzi M, Vavasori A (2008) J Mol Struct 858:46
Stephen H, Staskun B (1956) J Chem Soc 204:980
McCullough JD Jr, Curtin DY, Paul IC (1972) J Am Chem Soc 94:874
Jones B (1944) Chem Rev 35:335
Luca LD, Giacomelli G, Porcheddu A (2002) J Org Chem 67:6272
Furuya Y, Ishihara K, Yamamoto H (2005) J Am Chem Soc 127:11240
Wang B, Gu YL, Luo C, Yang T, Yang LM, Suo JS (2004) Tetrahedron Lett 45:3369
Ronchin L, Vavasori A, Bortoluzzi M (2008) Catal Commun 10:251
Ronchin L, Vavasori A (2009) J Mol Catal A 313:22
Zhang JS, Wang K, Lu YC, Luo GS (2012) AIChE J 58:925
Zhang JS, Wang K, Lu YC, Luo GS (2012) AIChE J 58:3156
Egberink H, Van Heerden C (1980) Anal Chim Acta 118:359
Nguyen MT, Raspoet G, Vanquickenborne LG (1997) J Am Chem Soc 119:2552
Acknowledgments
We gratefully acknowledge the supports of the National Natural Science Foundation of China (21036002, 21176136) and National Basic Research Program of China (2012CBA01203) on this work.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhang, J.S., Riaud, A., Wang, K. et al. Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam in a Modified Catalytic System of Trifluoroacetic Acid. Catal Lett 144, 151–157 (2014). https://doi.org/10.1007/s10562-013-1114-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-013-1114-3