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Low Environmental Load Process for the Beckmann Rearrangement of Cycloalkanone Oximes by Brønsted Acid Catalyst with Cobalt Salts

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DOI: 10.4236/ijoc.2015.53016    3,679 Downloads   4,320 Views   Citations

ABSTRACT

Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Yamamoto, H. , Komeda, M. , Ozaki, A. , Sumimoto, M. , Hori, K. and Sugimoto, T. (2015) Low Environmental Load Process for the Beckmann Rearrangement of Cycloalkanone Oximes by Brønsted Acid Catalyst with Cobalt Salts. International Journal of Organic Chemistry, 5, 147-152. doi: 10.4236/ijoc.2015.53016.

References

[1] Gawley, R.E. (2004) The Beckmann Reactions: Rearrangements, Elimination—Additions, Fragmentations, and Rearrangement—Cyclizations. Organic Reactions, 35, 1-420.
http://dx.doi.org/10.1002/0471264180.or035.01
[2] Smith, M.B. and March, J. (2007) March's Advanced Organic Chemistry. 6th Edition, John Wiley & Sons, Inc., Hoboken, 1613-1616.
[3] Kaur, N., Sharma, P. and Kishore, D. (2012) Application of Different Catalysts in Beckmann Rearrangement. Journal of Chemical and Pharmaceutical Research, 4, 1938-1946.
[4] Zhang, J.S., Riaud, A., Wang, K., Lu, Y.C. and Luo, G.S. (2014) Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam in a Modified Catalytic System of Trifluoroacetic Acid. Catalysis Letters, 144, 151-157.
http://dx.doi.org/10.1007/s10562-013-1114-3
[5] Rancan, E., Aricò, F., Quartarone, G., Ronchin, L., Tundo, P. and Vavasori, A. (2014) Self-Catalyzed Direct Amidation of Ketones: A Sustainable Procedure for Acetaminophen Synthesis. Catalysis Communications, 54, 11-16.
http://dx.doi.org/10.1016/j.catcom.2014.05.007
[6] Mao, D., Long, Z., Zhou, Y., Li, J., Wanga, X. and Wang J. (2014) Dual-Sulfonated Dipyridinium Phosphotungstate Catalyst for Liquid-Phase Beckmann Rearrangement of Cyclohexanone Oxime. RSC Advances, 4, 15635-15641.
http://dx.doi.org/10.1039/c4ra00552j
[7] Opanasenko, M., Shamzhy, M., Lamac, M. and Cejka, J. (2013) The Effect of Substrate Size in the Beckmann Rearrangement: MOFs vs. Zeolites. Catalysis Today, 204, 94-100.
http://dx.doi.org/10.1016/j.cattod.2012.09.008
[8] Vaschetto, E.G., Monti, G.A., Herrero, E.R., Casuscelli, S.G. and Eimer, G.A. (2013) Influence of the Synthesis Conditions on the Physicochemical Properties and Acidity of Al-MCM-41 as Catalysts for the Cyclohexanone Oxime Rearrangement. Applied Catalysis A General, 453, 391-402.
http://dx.doi.org/10.1016/j.apcata.2012.12.016
[9] Zuidhof, N.T., de Croon, M.H.J.M., Schouten, J.C. and Tinge, J.T. (2013) Beckmann Rearrangement of Cyclohexanone Oxime in a Microreactor Setup with Internal Recirculation. Chemical Engineering & Technology, 36, 1387-1394. http://dx.doi.org/10.1002/ceat.201300088
[10] Bellussi, G. and Perego, C. (2000) Industrial Catalytic Aspects of the Synthesis of Monomers for Nylon Production. CATTECH, 4, 4-16.
http://dx.doi.org/10.1023/A:1011905009608
[11] An, N., Tian, B.-X., Pi, H.-J., Eriksson, L.A. and Deng, W.-P. (2013) Mechanistic Insight into Self-Propagation of Organo-Mediated Beckmann Rearrangement: A Combined Experimental and Computational Study. The Journal of Organic Chemistry, 78, 4297-4302.
http://dx.doi.org/10.1021/jo400278c
[12] Maia, A., Albanese, D.C.M. and Landini, D. (2012) Cyanuric Chloride Catalyzed Beckmann Rearrangement of Ketoximes in Biodegradable Ionic Liquids. Tetrahedron, 68, 1947-1950.
http://dx.doi.org/10.1016/j.tet.2011.12.051
[13] Hashimoto, M., Obora, Y., Sakaguchi, S. and Ishii, Y. (2008) Beckmann Rearrangement of Ketoximes to Lactams by Triphosphazene Catalyst. The Journal of Organic Chemistry, 73, 2894-2897.
http://dx.doi.org/10.1021/jo702277g
[14] Shibamoto, A., Iwahama, T. and Nakano, T. (2008) PCT Int Appl No. 2008078642.
[15] Furuya, Y., Ishihara, K. and Yamamoto, H. (2005) Cyanuric Chloride as a Mild and Active Beckmann Rearrangement Catalyst. Journal of the American Chemical Society, 127, 11240-11241.
http://dx.doi.org/10.1021/ja053441x
[16] De Luca, L., Giacomelli, G. and Porcheddu, A. (2002) Beckmann Rearrangement of Oximes under Very Mild Conditions. The Journal of Organic Chemistry, 67, 6272-6274.
http://dx.doi.org/10.1021/jo025960d
[17] Kim, J., Park, W. and Ryoo, R. (2011) Surfactant-Directed Zeolite Nanosheets: A High-Performance Catalyst for Gas-Phase Beckmann Rearrangement. ACS Catalysis, 1, 337-341.
http://dx.doi.org/10.1021/cs100160g
[18] Komeda, M., Ozaki, A., Hayashi, K., Sumimoto, M., Hori, K., Sugimoto, T. and Yamamoto, H. (2015) The Effective Catalyst (Cobalt Salt/Lewis Acid) for Beckmann Rearrangement of Cycloalkanone Oximes to Lactams under Mild Conditions. International Journal of Organic Chemistry, 5, 57-62.
http://dx.doi.org/10.4236/ijoc.2015.52007
[19] Hori, K., Sumimoto, M. and Yamamoto, H. (2015) Unpublished Data.

  
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