Preparation of mono- and diacetyl 4,4′-dimethylbiphenyl and their corresponding carboxylic acids: Reactivity, selectivity and isomer distribution studies via Lewis acid catalyzed Friedel-Crafts acetylation/oxidation

A reactivity-selectivity study of the Friedel-Crafts acetylation of 3,3′-dimethylbiphenyl and the oxidation of the acetyl derivatives

“…In boiling nitromethane the yield was only 11.8% and the reaction was accompanied by the formation of a dark polymeric material. The low yield obtained in nitromethane is not unusual; it was observed also in previous studies of the acetylation of 4,4′-dimethylbiphenyl [11] and of 9H-fluorene [13]. When the reaction was carried out in boiling nitrobenzene acetylated products could only be detected in trace amounts.…”

“…The Friedel-Crafts acylation is a powerful and successful way to introduce new carbon-carbon bonds in aromatic compounds and is one of the most important one-step routes for the synthesis of aromatic ketones, in research laboratories and in the chemical and pharmaceutical industries [ 1 - 5 ]. Although the reaction has been known for more than 130 years it still receives attention [ 6 - 16 ] the recent interest being focused on the use of ionic liquids as solvents [ 7 ], selectivity studies [ 6 , 9 , 11 , 13 ], the application of solid catalysts [ 16 ], and still, mechanism details [ 8 , 12 , 14 , 15 ]. Simple aromatic hydrocarbons and methyl substituted derivatives have featured as substrates in both earlier and more recent studies of the reaction including benzenes [ 6 , 7 , 17 - 19 ], biphenyls and fluorene [ 11 , 13 , 20 ], naphthalenes [ 21 - 23 ], anthracenes [ 14 , 24 , 25 ], phenanthrenes [ 12 , 26 ], pyrenes [ 27 ], and chrysenes [ 28 ] and as a part of our continuing interest in Friedel-Crafts acetylations [ 11 , 13 , 21 , 28 - 31 ], we now report details of the acetylation of 3,3′-dimethylbiphenyl (3,3′-dmbp).…”

“…Although the reaction has been known for more than 130 years it still receives attention [ 6 - 16 ] the recent interest being focused on the use of ionic liquids as solvents [ 7 ], selectivity studies [ 6 , 9 , 11 , 13 ], the application of solid catalysts [ 16 ], and still, mechanism details [ 8 , 12 , 14 , 15 ]. Simple aromatic hydrocarbons and methyl substituted derivatives have featured as substrates in both earlier and more recent studies of the reaction including benzenes [ 6 , 7 , 17 - 19 ], biphenyls and fluorene [ 11 , 13 , 20 ], naphthalenes [ 21 - 23 ], anthracenes [ 14 , 24 , 25 ], phenanthrenes [ 12 , 26 ], pyrenes [ 27 ], and chrysenes [ 28 ] and as a part of our continuing interest in Friedel-Crafts acetylations [ 11 , 13 , 21 , 28 - 31 ], we now report details of the acetylation of 3,3′-dimethylbiphenyl (3,3′-dmbp). Compounds and materials derived from this building block are of particular interest in the field of molecular liquid crystals [ 31 ], polymers [ 32 , 33 ] and metal-complexes [ 34 ].…”

Synthesis of 3-acetyl-6-(o-methyl benzoyl)-N-ethylcarbazole

“…And the aluminum chloride in the formed complex could no longer catalyze acylation. So, in acylation reactions, theoretically, the dosage of aluminum chloride should be at least equimolar to the raw material, and, actually, it was 10-50% in excess of the equimolar dosage in many cases [6,7].…”