| DOI | Resolve DOI: https://doi.org/10.1021/ja00305a023 |
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| Author | Search for: Bunce, N.J.; Search for: Ingold, K. U.1; Search for: Landers, J.P.; Search for: Lusztyk, J.1; Search for: Scaiano, J.C.1 |
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| Affiliation | - National Research Council of Canada
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| Format | Text, Article |
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| Abstract | Five 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. |
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| Publication date | 1985 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21276765 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | f1180270-712d-467e-9c17-46966a39247e |
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| Record created | 2015-10-13 |
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| Record modified | 2020-03-17 |
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