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C-Methylation Of Organic Substrates: A Comprehensive Overview. Part Ii. Methanol As Methylating Agent. A Case Of Catalysis Versatility


Saad Moulay*   Pages 1 - 114 ( 114 )


The present account surveys the results of the myriad of works on C-methylation of organic substrates with methanol as an eco-friendly methylating agent. The innumerable reports on this issue reveal the widespread use of a set of solid catalysts such as molecular sieves, zeolites, metal phosphates, metal oxides and transition metal complexes, to accomplish such methylation. One related facet was the impact of the numbers of Brønstëd acid sites, of Lewis acid sites, and of Lewis base sites present in solid catalysts, such as zeolites, their ratios, and their strengths that affect the distribution of the methylation products and their selectivities. Also, specific surface area and porosity for some solid catalysts such as zeolites play additional roles in the overall reaction. Not only these properties of a catalyst that influence the methylation outcome but also the temperature, space velocity (WHSV, LHSV, GSHV), weight of catalyst per reactant flow rate (W/F), time of stream (TOS), and methanol/substrate molar ratio. The treated substrates herein discussed were aromatic hydrocarbons (benzene, biphenyls, naphthalenes, toluene, xylenes), alkenes, phenolics (phenol, cresols, anisole), N-heteroarenes, carbonyls, alcohols, and nitriles. Methylation of benzene affords not only toluene as main product but also polymethylated benzenes (xylenes, pseudocumene, hexamethylenebenzene, and also ethylbenzene as a sidechain product). Also, toluene is sensitive to the reaction conditions, giving rising to ring methylation and to sidechain one (ethylbenzene and styrene), besides the formation of benzene as a disproportionation product. Wealth of results from the methylation of phenolic compounds bears witness to the interest of different investigators in this special research. As to these phenolics, concurrent O-methylation inevitably parallels the C-methylation, and the selectivity of the latter one remains depended on the above-cited factors; ortho-cresol and 2,6-xylenol have been the main C-ring methylated phenols. Methylation of olefins with methanol over solid catalysts, leading to higher olefins, is of a great interest. The chemistry involved in the methylation of N-heteroarenes such as pyridines, indoles, and pyrroles is significant. Application of the methylation protocols, using methanol as a reagent and transition metal complexes as catalysts, to ketones, esters, aldehydes, nitriles, and alcohols, ends up with some important molecules such as acrylonitrile (a monomer) and isobutanol (a biofuel).


Alkenes, Benzene, Catalysts, N-Heteroarenes, Naphthalenes, Phenolics, Methylation, Methanol, Toluene


Laboratoire de Chimie-Physique Moléculaire et Macromoléculaire, Département de Génie des Procédés, Faculté de Technologie, Université Saâd Dahlab de Blida, B. P. 270, Route de Soumâa, 09000, Blida

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