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Iron(II, III)-catalyzed oxidativeN-dealkylation of amines with dioxygen

Authors
Journal
Journal of Molecular Catalysis A Chemical
1381-1169
Publisher
Elsevier
Publication Date
Volume
212
Identifiers
DOI: 10.1016/j.molcata.2003.11.018
Keywords
  • N-Demethylation
  • N-Dealkylation
  • Dioxygen Activation
  • Alkylated Amines
  • Iron Complexes

Abstract

Abstract Labile iron complexes (e.g., [Fe III(bpy) 2] MeCN 3+, [Fe II(bpy) 2] MeCN 2+, [Fe III(H 2O) 6] MeCN 3+, and [Fe II(H 2O) 6] MeCN 2+) in base-free acetonitrile activate dioxygen for the direct oxygenation of N,N- and N-alkylated amines to form N-dealkylated products and corresponding aldehydes. N,N-dimethylaniline (DMA) is oxidized to N-methylaniline (MA) and formaldehyde as well as to N-methylanilide. Formaldehyde and the excess of substrate undergo condensation reaction to produce 4,4′-methylenebis( N,N-dimethylaniline) (MBDME). Small amounts of N-methylformanilide (MF) and formanilide are also formed during oxidation of N,N-dimethylaniline and N-methylaniline respectively. Iron(III) catalysts are reduced by the substrate to iron(II), which activates dioxygen. Dioxygen activation step is preceded by the equilibrium reaction between iron(II) catalyst and substrate.

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