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

Abstract

Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO 2-supported gold nanoparticles (Au/CeO 2) and Aerosil 200 in the presence of an atmosphere of O 2. 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/CeO 2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

Authors:
 [1];  [2];  [2];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1335038
Report Number(s):
IS-J-9155
Journal ID: ISSN 1011-372X; PII: 1834
Grant/Contract Number:
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Catalysis Letters
Additional Journal Information:
Journal Volume: 146; Journal Issue: 11; Journal ID: ISSN 1011-372X
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; lactams; nanogold; ceria; cyclic amines; oxidation; amine oxidation

Citation Formats

Dairo, Taiwo O., Nelson, Nicholas C., Slowing, Igor I., Angelici, Robert J., and Woo, L. Keith. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold. United States: N. p., 2016. Web. doi:10.1007/s10562-016-1834-2.
Dairo, Taiwo O., Nelson, Nicholas C., Slowing, Igor I., Angelici, Robert J., & Woo, L. Keith. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold. United States. doi:10.1007/s10562-016-1834-2.
Dairo, Taiwo O., Nelson, Nicholas C., Slowing, Igor I., Angelici, Robert J., and Woo, L. Keith. Fri . "Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold". United States. doi:10.1007/s10562-016-1834-2. https://www.osti.gov/servlets/purl/1335038.
@article{osti_1335038,
title = {Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold},
author = {Dairo, Taiwo O. and Nelson, Nicholas C. and Slowing, Igor I. and Angelici, Robert J. and Woo, L. Keith},
abstractNote = {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.},
doi = {10.1007/s10562-016-1834-2},
journal = {Catalysis Letters},
number = 11,
volume = 146,
place = {United States},
year = {Fri Sep 23 00:00:00 EDT 2016},
month = {Fri Sep 23 00:00:00 EDT 2016}
}

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