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Author(s):   Lisowski, C.E.; Duncan, J.R.; Ranieri, A.J.; Heard, G.L.; Setser, D.W.; Holmes, B.E.
Title:   Isomerization of Neopentyl Chloride and Neopentyl Bromide by a 1,2-Interchange of a Halogen Atom and a Methyl Group
Journal:   J. Phys. Chem. A
Volume:   114
Page(s):   10395 - 10402
Year:   2010
Reference type:   Journal article
Squib:   2010LIS/DUN10395-10402

Reaction:   tert-C4H9 + ·CH2Cl(CH3)2C=CHCH3 + HCl
Reaction order:   2
Temperature:   298 K
Pressure:  4.00E-6 - 1.33E-4 bar
Rate expression:   no rate data available
Category:  Experiment
Data type:   Mechanistic information only
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Direct photolysis
Time resolution:   By end product analysis
Analytical technique:   Gas chromatography
Comments:   The recombination of chloromethyl and t-butyl radicals at room temperature was used to generate neopentyl chloride molecules with 89 kcal mol-1 of internal energy. The observed unimolecular reactions, which give 2-methyl-2-butene and 2-methyl-1-butene plus HCl, as products, are explained by a mechanism that involves the interchange of a methyl group and the chlorine atom to yield 2-chloro-2-methylbutane, which subsequently eliminates hydrogen chloride by the usual four-centered mechanism to give the observed products. The interchange isomerization process is the rate-limiting step. Similar experiments were done with CD2Cl and C(CH3)3 radicals to measure the kinetic-isotope effect to help corroborate the proposed mechanism.

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