Kinetic study of the photochlorination of 2,3-dimethylbutane and other alkanes in solution in the presence of benzene. First measurements of the absolute rate constants for hydrogen abstraction by the "free" chlorine atom and the chlorine atom-benzene π-complex. Identification of these two species as the only hydrogen abstractors in these systems

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  1. Get@NRC: Kinetic study of the photochlorination of 2,3-dimethylbutane and other alkanes in solution in the presence of benzene. First measurements of the absolute rate constants for hydrogen abstraction by the "free" chlorine atom and the chlorine atom-benzene π-complex. Identification of these two species as the only hydrogen abstractors in these systems (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/ja00305a023
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume107
Issue19
Pages54645472; # of pages: 9
AbstractFive photochemical sources have been employed to generate chlorine atoms in solution in the presence of benzene at room temperature. The chlorine atoms react with benzene (k 3 = 6.0 × 10 9 M -1 s -) to form a species which is firmly identified as the C 6H 6Cl· π-complex, 1. Laser flash photolytic techniques have been employed to measure absolute rate constants for hydrogen atom abstraction from various alkanes by 1. This species proved to have a reactivity less than that of the "free" chlorine atom but greater than that of the tert-butoxyl radical. These absolute rate constants are in satisfactory agreement with the results of competitive chlorinations of certain alkanes in benzene solvent. Absolute rate constants were also measured for the reaction of the "free" chlorine atom with 2,3-dimethylbutane (DMB). A reasonably comprehensive study of the tertiary/primary selectivity for chlorination of DMB over a range of concentrations and in a variety of benzene/CCl 4 mixtures has been carried out. It is shown that this DMB selectivity data can be quantitatively described by a kinetic scheme which involves hydrogen abstraction by only two species, "free" Cl· atoms and 1.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276765
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Record identifierf1180270-712d-467e-9c17-46966a39247e
Record created2015-10-13
Record modified2016-05-09
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