The Friedel–Crafts acetylation of naphthalene in 1,2-dichloroethane solution. Kinetics and mechanism

Dowdy, David W.; Gore, P. H.; Waters, D. N.

doi:10.1039/p29910001149

Cited by 22 publications

(15 citation statements)

References 23 publications

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“…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 ].…”

Section: Resultsmentioning

confidence: 99%

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

Titinchi

Kamounah

Abbo

et al. 2012

Chemistry Central Journal

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BackgroundFriedel-Crafts acetylation is an important route to aromatic ketones, in research laboratories and in industry. The acetyl derivatives of 3,3′-dimethylbiphenyl (3,3′-dmbp) have applications in the field of liquid crystals and polymers and may be oxidized to the dicarboxylic acids and derivatives that are of interest in cancer treatment.FindingsThe effect of solvent and temperature on the selectivity of monoacetylation of 3,3’-dmbp by the Perrier addition procedure was studied using stoichiometric amounts of reagents. 4-Ac-3,3′-dmbp was formed almost quantitatively in boiling 1,2-dichloroethane and this is almost twice the yield hitherto reported. Using instead a molar ratio of substrate:AcCl:AlCl3 equal to 1:4:4 or 1:6:6 in boiling 1,2-dichloroethane, acetylation afforded 4,4′- and 4,6′-diacetyl-3,3′-dmbp in a total yield close to 100%. The acetyl derivatives were subsequently converted to the carboxylic acids by hypochlorite oxidation. The relative stabilities of the isomeric products and the corresponding σ-complexes were studied by DFT calculations and the data indicated that mono- and diacetylation followed different mechanisms.ConclusionsFriedel-Crafts acetylation of 3,3′-dmbp using the Perrier addition procedure in boiling 1,2-dichloroethane was found to be superior to other recipes. The discrimination against the 6-acetyl derivative during monoacetylation seems to reflect a mechanism including an AcCl:AlCl3 complex or larger agglomerates as the electrophile, whereas the less selective diacetylations of the deactivated 4-Ac-3,3′-dmbp are suggested to include the acetyl cation as the electrophile. The DFT data also showed that complexation of intermediates and products with AlCl3 does not seem to be important in determining the mechanism.

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Section: Resultsmentioning

confidence: 99%

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

Titinchi

Kamounah

Abbo

et al. 2012

Chemistry Central Journal

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“…6 The pattern of irreversibility of Friedel-Cras acylations has been highlighted under classical experimental conditions, (AlCl 3 , a trace of water) e.g., in the naphthalene series. [6][7][8] The incursion of reversibility in Friedel-Cras acylation was revealed in 1974 by Agranat et al in the benzoylation of naphthalene in polyphosphoric acid (PPA) at elevated temperatures. 9 The kinetically controlled 1-benzoylnaphthalene rearranged to the thermodynamically controlled 2-benzoylnaphthalene (PPA, 140 C), whereas the latter underwent only deacylation to give naphthalene.…”

Section: Introductionmentioning

confidence: 99%

Reversible Friedel–Crafts acyl rearrangements of planar polycyclic aromatic ketones: dibenzofluorenones

et al. 2013

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“…This is in accordance with best literature yield and selectivity. 9,10 It has been suggested that the position of attack on naphthalene is determined to a large extent by steric factors. 11 For example, if the reaction is carried out in nitrobenzene or nitromethane, 11 the 2-isomer is the major product and the acylating agent is thought to be an AcCl-AlCl 3 -nitrobenzene complex.…”

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confidence: 99%

“…Simple aromatic compounds, such as toluene, anisole or chlorobenzene are easily acetylated in yields that are equal to the best literature yields. [9][10][11][12][13][14] In addition, the regiochemical control of these reactions is excellent. In the acetylation of electron-rich polyaromatics, there is evidence that the reaction is reversible and that deacetylation reactions are proton catalysed.…”

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Friedel–Crafts reactions in room temperature ionic liquids

Earle¹,

Seddon²,

Adams³

et al. 1998

Chem. Commun.

106

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Friedel-Crafts reactions in the ionic liquid system 1-methyl-3-ethylimidazolium chloride-aluminium(III) chloride can be performed with excellent yields and selectivities, and in the case of anthracene, have been found to be reversible.The possibility of carrying out chemical transformations in low temperature ionic liquids has, to date, received little attention. 1 Ionic liquids such as the [emim]Cl-AlCl 3 ([emim] + = 1-methyl-3-ethylimidazolium cation) system have been shown to demonstrate catalytic activity in reactions such as Friedel-Crafts acylations, 2,3 alkylation reactions, 4 isomerisation of alkanes, 5 and the alkylation of isobutane with butene. 6 Here, we present a series of reactions of AcCl with carbocyclic aromatic compounds in acidic compositions (X = 0.67) ‡ of [emim]Cl-AlCl 3 (Fig. 1) and compare their performance with similar reactions in 'conventional' molecular solvents.

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The Friedel–Crafts acetylation of naphthalene in 1,2-dichloroethane solution. Kinetics and mechanism

Cited by 22 publications

References 23 publications

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

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

Reversible Friedel–Crafts acyl rearrangements of planar polycyclic aromatic ketones: dibenzofluorenones

Friedel–Crafts reactions in room temperature ionic liquids

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