Aluminium chloride as a solvo acid and friedel-crafts catalyst

Huston, John L.; Lang, C.E.

doi:10.1016/0022-1902(57)80105-5

Cited by 8 publications

(2 citation statements)

References 12 publications

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“…In previous publications we have considered the two mechanisms which appear possible for the benzoylation reaction,9•10 a direct reaction of the aromatic with the addition complex or a prior ionization of the complex followed by reaction of the aromatic with the ion-pair intermediates.19•20 The present data do not distinguish between these mechanisms.21 A complete understanding of the aluminum chloride-catalyzed acylation mechanism requires a better understanding of the structures of the acyl chloride-aluminum chloride com-plexes22•23 as well as information as to the extent and rate of ionization of these complexes in various reaction media. 24 The reaction of benzoyl bromide-aluminum bromide with toluene appears to be essentially identical with the related reaction of the chlorine derivative. The kinetics are the same, the rate constants exhibit the same change with initial complex concentration, and the actual second-order rate constants differ by only a small factor (20%).…”

Section: Discussionmentioning

confidence: 84%

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2

Jensen¹,

Marino²,

Brown³

1959

J. Am. Chem. Soc.

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Section: Discussionmentioning

confidence: 84%

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2

Jensen¹,

Marino²,

Brown³

1959

J. Am. Chem. Soc.

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“…In molten GaGlg-POClg, however, POCl2+ ions seem to exist.61 A solvated cation with tetrahedral coordination of phosphorus is likely to exist in phosphorus oxychloride solutions Accordingly radiochlorine exchange reactions between tetramethylammonium chloride and the solvents take place instantaneously in nitrosyl-chloride23 and phosphorus oxychloride,62 as well as in related solvents such as thionyl chloride,6215•63 selenium oxychloride6215 and to some extent even between carbonyl chloride and aluminum chloride. 64 Lewis and Sowerby62a have concluded that POOLions exist in solutions of phosphorus oxychloride by comparing rates of radiochlorine exchange between Et4NCl and POCl3 in phosphorus oxychloride, chloroform, nitrobenzene and acetonitrile, but no direct proof has been obtained. The T-x diagram of the system Et4NCl-POCl3 gives no indication for compound formation, but Lewis and Sowerby62a observed that POCl3 cannot be completely removed from the solution even in a vacuum for many days.…”

Section: Cl-mentioning

confidence: 99%

Ionic Reactions in Solutions of Certain Chlorides and Oxychlorides

Gutmann¹

1959

J. Phys. Chem.

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Does not sensitivity to low acetone concentration suggest effect on sensitive property of water•-e.g., surface tension-or even on nature of solution of complexes with large organic groups in water?. N. Neumann.-In looking for correlations between the properties of ions of this type and properties of the solvent mixture we have been influenced by data on the rates of dissociation of Ni(phen)32+, Fe(phen)32+ and Fe(bipy)32+ in organic-water mixtures (unpublished work of Dr. Lester Seiden). These rates show a minimum as would be expected if the behavior correlated with the viscosity. The surface tension decreases continuously on going from water to acetone, and would not lead one to expect a minimum in the rate. It seems reasonable that the rearrangement of solvent molecules would be a simpler process in the case of dissociation of a single ion than in the case of bringing two ions together, hence correlation with the dissociation data seemed more promising. It is true that the exchange re-sults considered alone show greater similarity to the surface tension than to the viscosity.Henry S. Frank.-Dr. Katzin's suggestion about surface tension may be paraphrased in more general terms by referring to the influence which non-polar groups have on water structure. For example, tetra-n-butylammonium ion affects water in such a way as to produce over 120 units of excess heat capacity beyond what can be accounted for on the basis of additivity rules. If we interpret this as an influence of the hydrophobic nature of the alkyl groups the same influence might be expected to produce a sorting tendency in mixed solvents, attracting, say, acetone, into nearest-neighbor positions, in contrast to the customary dielectric salting out effect. Something similar might happen with the tris-phenanthroline complexes, and this could account for the shape of the curve of the effect of additions of acetone.

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The Friedel‐Crafts Acylation Reaction I. Substituent Effect in the Friedel‐Crafts Benzoylation of Toluene

Slootmaekers¹,

Roosen²,

Verhulst³

1962

Bulletin des Soc Chimique

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On a mesur6 les constantes de vitesse de la reaction de Friedel et Crafts de chlorures de benzoyle, substitu6s en para, sur le toluene et dam le chloro-W n e c o m e solvant. Des valeurs obtenues A diff6rentes temperatures on a dkduit les parametres cin6tiques des r&ctims : p.X-; ks.104 1.mole-l sec-l B 20oC; AH* kcal/mole; As* u.e. : t.Bu-: 0,63; 14,7; -27,3; Me-; 0,83; -28,O; Br-; 6,77; 13,3; -27,2. 1'6quation de Hammett. On prouve que cela ne peut etre attribu6 B un changement dans la distribution des isomers ou dans le mkanisme de la reaction pour les d86rents membres de la skrie. I1 est possible qu'une relation linkire relie I'enthalpie B I'entropie d'activation de la reaction, mais les rbultats ne sont pas convaincants. La constante de vitesse dkpend de la concentration initiale en complexe reactionnel. Les valeurs de la constante de vitesse obtenues par extrapolation vers m e dilution inhie n'obkissent non plus h 1'6quation de Hammett. Ceci est probablement dQ B l'emploi de la concentration du r k t i f c o m e paramktre d'extrapolation au lieu d'une propri6t6 physique du m6lange rkctionnel. Les reactions sont suivies par titration de l'acide chlorhydrique form6 dans la rkrion et entrain6 dans un courant de gaz inerte. Cette mkthode exp6rimentale est discuth et d h i t e en detail.

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Aluminium chloride as a solvo acid and friedel-crafts catalyst

Cited by 8 publications

References 12 publications

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2

Ionic Reactions in Solutions of Certain Chlorides and Oxychlorides

The Friedel‐Crafts Acylation Reaction I. Substituent Effect in the Friedel‐Crafts Benzoylation of Toluene

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Aluminium chloride as a solvo acid and friedel-crafts catalyst

Cited by 8 publications

References 12 publications

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides1,2

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides1,2

Ionic Reactions in Solutions of Certain Chlorides and Oxychlorides

The Friedel‐Crafts Acylation Reaction I. Substituent Effect in the Friedel‐Crafts Benzoylation of Toluene

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Product

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Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2

Kinetics of the Reaction of Benzoyl Halides with Toluene in Non-polar Solvents under the Influence of Aluminum Halides^1,2