The kinetic behaviour and the product distributions of brominations of several arylalkynes with Br(2) in the room-temperature ionic liquids (ILs) 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF(6)] and 1-butyl-3-methylimidazolium. bromide [bmim]Br, have been investigated at different temperatures. In [bmim]Br, alkynes stereospecifically gave the anti addition products, the reactions following a second-order rate law. In [bmim][PF(6)], mixtures of syn and anti addition products were obtained, and the reactions followed a second- or third-order rate law, depending on the structure of the alkyne and the concentration of Br(2). The data obtained for the reactions in [bmim]Br are interpreted on the basis of a mechanism involving a product- and a rate-determining nucleophilic attack by bromide on the alkyne-Br(2) pi complex. The data relating to the electrophilic addition in [bmim][PF6] are explained in terms of the initial formation of a 1:1 alkyne-Br(2) pi complex, the ionisation of which, probably catalysed either by a second halogen molecule or by the imidazolium cation, gives a bromirenium (or beta-bromovinyl cation) Br(-) or [Br(3)](-) intermediate. Such intermediates then collapse to give the corresponding dibromo adduct(s). The kinetic constants and the activation parameters for the reaction in [bmim]Br are compared with those relating to the second-order reaction of the same alkynes with tetrabutylammonium tribromide ([NBu(4)][Br(3)]) in 1,2-dichloroethane (DCE). On the basis of the kinetic data, a significant role for solvent viscosity in determining the reaction rate may be envisaged. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Bromination of alkynes in ionic liquids - A kinetic investigation
CHIAPPE, CINZIA;
2002-01-01
Abstract
The kinetic behaviour and the product distributions of brominations of several arylalkynes with Br(2) in the room-temperature ionic liquids (ILs) 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF(6)] and 1-butyl-3-methylimidazolium. bromide [bmim]Br, have been investigated at different temperatures. In [bmim]Br, alkynes stereospecifically gave the anti addition products, the reactions following a second-order rate law. In [bmim][PF(6)], mixtures of syn and anti addition products were obtained, and the reactions followed a second- or third-order rate law, depending on the structure of the alkyne and the concentration of Br(2). The data obtained for the reactions in [bmim]Br are interpreted on the basis of a mechanism involving a product- and a rate-determining nucleophilic attack by bromide on the alkyne-Br(2) pi complex. The data relating to the electrophilic addition in [bmim][PF6] are explained in terms of the initial formation of a 1:1 alkyne-Br(2) pi complex, the ionisation of which, probably catalysed either by a second halogen molecule or by the imidazolium cation, gives a bromirenium (or beta-bromovinyl cation) Br(-) or [Br(3)](-) intermediate. Such intermediates then collapse to give the corresponding dibromo adduct(s). The kinetic constants and the activation parameters for the reaction in [bmim]Br are compared with those relating to the second-order reaction of the same alkynes with tetrabutylammonium tribromide ([NBu(4)][Br(3)]) in 1,2-dichloroethane (DCE). On the basis of the kinetic data, a significant role for solvent viscosity in determining the reaction rate may be envisaged. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
