Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

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

doi:10.1007/s10562-016-1834-2

Title: Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

Journal Article · Fri Sep 23 00:00:00 EDT 2016 · Catalysis Letters

DOI:https://doi.org/10.1007/s10562-016-1834-2· OSTI ID:1335038

Dairo, Taiwo O. ^[1]; Nelson, Nicholas C. ^[2]; Slowing, Igor I. ^[2]; Angelici, Robert J. ^[1]; Woo, L. Keith ^[1]

Iowa State Univ., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)

Here, 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.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1335038

Report Number(s):: IS-J-9155; PII: 1834

Journal Information:: Catalysis Letters, Vol. 146, Issue 11; ISSN 1011-372X

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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amine oxidation

Title: Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

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