The Selective Alkylation of Aniline with Methanol over ZSM-5 Zeolite

Chen, P.Y.; Chen, H.C.; Chu, Hsin-Sen; Chang, N.S.; Chuang, T.K.

doi:10.1016/s0167-2991(09)60942-3

Cited by 35 publications

(8 citation statements)

References 13 publications

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“…Currently, N-alkylation of aromatic amines with alkylating agents to produce N-alkyl arylamines is accompanied by the great challenge of the rigorous requirements for the equipment, hard purification of the products, and treatment of the waste water due to the occurrence of N,N-dialkylation using mineral acid, H 2 SO 4 , H 3 PO 4 , and hydrochloride as catalysts [6,7] . Gas-phase N-alkylation of aromatic amine using zeolites (ZSM-5, KY, NaX, CaY) [8][9][10][11] , metallic oxide [12][13][14] or metallic salt [12,15] instead of mineral acids as catalysts may avoid the equipment corrosion, but it is difficult to obtain an ideal selectivity for the desired product. Furthermore, the high reaction temperature leads to the deactivation of the catalyst and a decreased selectivity for the target product.…”

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confidence: 99%

One pot synthesis of N-ethylaniline from nitrobenzene and ethanol

Zhang

Xiang

et al. 2008

Sci. China Ser. B-Chem.

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A novel method for the one pot synthesis of N-alkyl arylamines from nitro aromatic compounds and alcohols is proposed through the combination of the aqueous-phase reforming of alcohol for hydrogen production, the reduction of nitro aromatic compounds for the synthesis of aromatic amine and the N-alkylation of aromatic amine for the production of N-alkyl arylamine over an identical catalyst under the same conditions of temperature and pressure in a single reactor. In this process, hydrogen generated from the aqueous-phase reforming of alcohols was used in-situ for the hydrogenation of nitro aromatic compounds for aromatic amine synthesis, followed by N-alkylation of aromatic amine with alcohols to form the corresponding N-alkyl arylamines at a low partial pressure of hydrogen. For the system composed of nitrobenzene and ethanol, under the conditions of 413 K and P N 2 = 1 MPa, the conversion degrees of nitrobenzene and aniline were 100%, the selectivity to N-ethylaniline and N, N-diethylaniline were 85.9% and 0%-4%, respectivity, after reaction for 8 h at the volumetric ratio of nitrobenzene : ethanol : water = 10 : 60 : 0. The selectivity for N, N-diethylaniline production is much lower than that through the traditional method. In this process, hydrogen and aromatic amines generated from the aqueous-phase reforming of alcohols and hydrogenation of nitro aromatic compounds, respectively, could be promptly removed from the surface of the catalyst due to the occurrence of in-situ hydrogenation and N-alkylation reactions. Thus, this may be a potential approach to increase the selectivity to N-alkyl arylamine.

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confidence: 99%

One pot synthesis of N-ethylaniline from nitrobenzene and ethanol

Zhang

Xiang

et al. 2008

Sci. China Ser. B-Chem.

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“…Zeolites X and Y exchanged with Li and Na cations give rise to C-methylation products in this reaction [108]. ZSM-5 catalyzes both C-and N-methylation of aniline [118]. Thus, a halide cluster proved to be a selective catalyst for the N-methylation of an aromatic amine with methanol.…”

Section: N-alkylation Of Amine (Equationmentioning

confidence: 98%

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Nagashima

Kamiguchi

Chihara

2014

Metals

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Halide clusters of Group 5-7 metals develop catalytic activity above 150-250 °C, and the activity is retained up to 350-450 °C by taking advantage of their thermal stability, low vapor pressure, and high melting point. Two types of active site function: the solid Brønsted acid site and a coordinatively unsaturated site that catalyzes like the platinum metals do. Various types of catalytic reactions including new reactions and concerted catalyses have been observed over the clusters: hydrogenation, dehydrogenation, hydrogenolysis, isomerization of alkene and alkyne, and alkylation of toluene, amine, phenol, and thiol. Ring-closure reactions to afford quinoline, benzofuran, indene, and heterocyclic common rings are also catalyzed. Beckmann rearrangement, S-acylation of thiol, and dehydrohalogenation are also catalyzed. Although the majority of the reactions proceed over conventional catalysts, closer inspection shows some conspicuous features, particularly in terms of selectivity. Halide cluster catalysts are characterized by some aspects: cluster counter anion is too large to abstract counter cation from the protonated reactants, cluster catalyst is not poisoned by halogen and sulfur atoms. Among others, cluster catalysts are stable at high temperatures up to 350-450 °C. At high temperatures, apparent activation energy decreases, and hence weak acid can be a catalyst without decomposing reactants. OPEN ACCESSMetals 2014, 4 236

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“…The main factors influencing activity and selectivity are number and strength of acid site in the catalyst, shape selectivity of catalyst and reaction conditions. However, it was demonstrated [15,[23][24][25] that the use of strong solid acids with high concentration of Bronsted acid sites may not be suitable for this reaction. Weak to moderate strength of acid sites have been agreed to be involved in the reaction mechanism and the process being favored by the presence of Lewis acid sites.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of N-methylaniline by Aniline Alkylation with Methanol over Sn-MFI Molecular Sieve

et al. 2009

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Sn-MFI molecular sieves (Tin silicalite-1) with SiO 2 /SnO 2 molar ratio of 50-150 were synthesized and characterized. Elemental analysis, XRD and DRUV-vis confirmed that prepared samples were of MFI zeolite structure and Sn was incorporated in MFI framework. Vapor phase methylation of aniline over Sn-MFI was systematically studied and optimizations of process parameters were carried out. Sn-MFI (SiO 2 /SnO 2 = 50) was found to be optimum catalyst with 55% aniline conversion and 60% N-methylaniline selectivity. At lower space velocity (higher contact time) of 1 h -1 , aniline conversion was found to be increased to 71% with reduction in N-methylaniline selectivity to 39% and increased in N,N-dimethylaniline selectivity to 58%. The reaction follows first order kinetics with respect to aniline having activation energy of 7.3 kcal/mol.

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The Selective Alkylation of Aniline with Methanol over ZSM-5 Zeolite

Cited by 35 publications

References 13 publications

One pot synthesis of N-ethylaniline from nitrobenzene and ethanol

One pot synthesis of N-ethylaniline from nitrobenzene and ethanol

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Synthesis of N-methylaniline by Aniline Alkylation with Methanol over Sn-MFI Molecular Sieve

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