Abstract
Methylation of aniline is an industrially important process, aimed at the synthesis of mono-N-methylaniline (NMA), di-N-methylaniline (NNDMA) and toluidines which are useful raw materials for organic syntheses as well as important intermediates in the dye-stuff production and in the pharmaceutical and agrochemical industries. Up till now, industrial processes leading to these products are based on the application of corrosive liquid acids as catalysts [1,2] and should be replaced by environmentally more benign processes using solid catalysts such as oxides, clays and zeolites. It is known that alkylation of aniline may take place on acidic [3–6] and on basic zeolites [7,8]. Moreover, this reaction was performed even on zeolites with redox properties [3,9,10]. A detailed study of reaction mechanisms over zeolite catalysts pointed to existence of two mechanistic pathways: on acidic catalysts, the reaction proceeds via a methanol dehydration leading to surface methoxy groups as intermediates of N- alkylation, while on basic and redox catalysts, the reaction pathway includes methanol dehydrogenation leading to formaldehyde species, alkylation of aniline with formaldehyde to give N-methyleneaniline and hydrogenation of N- methyleneaniline to N-methylaniline [11–12]. In this contribution, aniline methylation has been studied on various molecular sieve catalysts. The effects of both catalyst structure and nature of active sites were investigated. The catalyst structures selected covered a broad range of pore sizes from 5.5 Å to 30 Å. The nature of the active sites was altered to obtain acidic, basic and redox materials.
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Ponomoreva, O.A., Knyazeva, E.E., Yuschenko, V.V., Ivanova, I. (2002). Aniline Methylation Over Modified Micro- And Mesoporous Catalysts. In: Derouane, E.G., Parmon, V., Lemos, F., Ribeiro, F.R. (eds) Principles and Methods for Accelerated Catalyst Design and Testing. NATO Science Series, vol 69. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0554-8_31
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DOI: https://doi.org/10.1007/978-94-010-0554-8_31
Publisher Name: Springer, Dordrecht
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