One-pot synthesis of N,N-dimethylaniline from nitrobenzene and methanol

A route for the direct synthesis of N,N-dimethylaniline from nitrobenzene and methanol was developed through the sequential coupling of the hydrogen production from methanol, hydrogenation of nitrobenzene to produce aniline, and N-methylation of aniline over a pretreated Raney-Ni® catalyst (at 443 K in methanol). A high yield of N,N-dimethylaniline up to 98% was obtained by the proposed methodology. In this process, aniline was produced from in-situhydrogenation of nitrobenzene with hydrogen generated from methanol, or transfer hydrogenation of nitrobenzene with methanol as donor, while methanol acted as a hydrogen source, alkylating reagent and solvent, simultaneously. Additionally, a plausible mechanism of this one-pot reaction process has been described.

[1]  J. Figueiredo,et al.  Hydrogenation of nitrobenzene over nickel nanoparticles stabilized by filamentous carbon , 2008 .

[2]  A. Perosa,et al.  Sequential Coupling of The Transesterification of Cyclic Carbonates with The Selective N-Methylation of Anilines Catalysed by Faujasites , 2008 .

[3]  Ying Bai,et al.  One pot synthesis of N-ethylaniline from nitrobenzene and ethanol , 2008 .

[4]  L. Bieber,et al.  Reductive methylation of primary and secondary amines and amino acids by aqueous formaldehyde and zinc , 2007 .

[5]  Li Xiaonian,et al.  A novel liquid system of catalytic hydrogenation , 2007 .

[6]  James A. Dumesic,et al.  A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts , 2005 .

[7]  R. V. Chaudhari,et al.  Selective synthesis of N,N-dimethyl aniline derivatives using dimethyl carbonate as a methylating agent and onium salt as a catalyst , 2005 .

[8]  James A. Dumesic,et al.  Aqueous-phase reforming of oxygenated hydrocarbons over Sn-modified Ni catalysts , 2004 .

[9]  J. Dumesic,et al.  Catalytic reforming of oxygenated hydrocarbons for hydrogen with low levels of carbon monoxide. , 2003, Angewandte Chemie.

[10]  A. Sacco,et al.  Selective N,N-methylation of aniline over cocrystallized zeolites RHO and zeolite X (FAU) and over Linde type L (Sr,K-LTL) , 2003 .

[11]  G. Huber,et al.  Raney Ni-Sn Catalyst for H2 Production from Biomass-Derived Hydrocarbons , 2003, Science.

[12]  S. Sivasanker.  12 Design of solid base catalysts for the production of chemicals , 2003 .

[13]  J. Dumesic,et al.  Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water , 2002, Nature.

[14]  Pietro Tundo,et al.  The chemistry of dimethyl carbonate. , 2002, Accounts of chemical research.

[15]  H. Sixta,et al.  A SOLVENT-FREE AND FORMALIN-FREE ESCHWEILER-CLARKE METHYLATION FOR AMINES , 2002 .

[16]  A. Romero,et al.  Catalytic activity, deactivation and re-use of Al-MCM-41 for N-methylation of aniline , 2002 .

[17]  F. Bautista,et al.  N-Alkylation of aniline with methanol over AlPO 4 Al 2O 3 catalysts , 1998 .

[18]  G. Verardo,et al.  New N‐permethylations and introduction of deuterium labelled methyl groups into primary and secondary amines , 1987 .

[19]  R. Johnstone,et al.  Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds , 1985 .

[20]  R. Johnstone,et al.  Metal-assisted reactions. Mechanism in heterogeneous catalytic transfer reduction , 1984 .

[21]  E. J. Kohn,et al.  Raney Nickel Catalyzed N-Alkylation of Aniline and Benzidine with Alcohols , 1955 .

[22]  H. Adkins,et al.  THE USE OF NICKEL AS A CATALYST FOR HYDROGENATION , 1930 .