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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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