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

被引：28

作者：

Naróg, D ^{[1
]}

Lechowicz, U ^{[1
]}

Pietryga, T ^{[1
]}

Sobkowiak, A ^{[1
]}

机构：

[1] Rzeszow Univ Technol, PL-35959 Rzeszow, Poland

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2004年 / 212卷 / 1-2期

关键词：

N-demethylation; N-dealkylation; dioxygen activation; alkylated amines; iron complexes;

D O I：

10.1016/j.molcata.2003.11.018

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Labile iron complexes (e.g., [Fe-III (bPY)(2)](MecN)(3+), [Fe-II(bPY)(2)](MeCN)(3+), and [Fe-III (H2O)(6)](MeCN)(3+), and [Fe-II(H2O)(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(NN-dimethylaniline) (MBDME). Small amounts of N-methylformanilide (MF) and formanilide are also formed during oxidation of NN-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. (C) 2003 Elsevier B.V. All rights reserved.

引用

页码：25 / 33

页数：9

共 95 条

[1] Kinetic deuterium isotope effect profiles and substituent effects in the oxidative N-demethylation of N,N-dimethylanilines catalyzed by tetrakis(pentafluorophenyl)porphyrin iron(III) chloride [J].