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Catalysis Letters

, Volume 146, Issue 11, pp 2278–2291 | Cite as

Aerobic Oxidation of Cyclic Amines to Lactams Catalyzed by Ceria-Supported Nanogold

  • Taiwo O. Dairo
  • Nicholas C. Nelson
  • Igor I. Slowing
  • Robert J. Angelici
  • L. Keith Woo
Article

Abstract

The oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

Graphical Abstract

Keywords

Lactams Nanogold Ceria Cyclic amines Oxidation Amine oxidation 

Notes

Acknowledgments

This research was partially supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences through the Ames Laboratory (Contract No. DE-AC02-07CH11358). The authors thank Evonik Degussa Corporation for a generous donation of Aerosil 200.

Supplementary material

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Supplementary material 1 (PDF 2931 KB)

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Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Taiwo O. Dairo
    • 1
  • Nicholas C. Nelson
    • 1
    • 2
  • Igor I. Slowing
    • 1
    • 2
  • Robert J. Angelici
    • 1
  • L. Keith Woo
    • 1
  1. 1.Department of ChemistryIowa State UniversityAmesUSA
  2. 2.U.S. D.O.E. Ames LaboratoryAmesUSA

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