Isomerization of neopentyl chloride and neopentyl bromide by a 1,2-interchange of a halogen atom and a methyl group.
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 CD(2)Cl and C(CH(3))(3) radicals to measure the kinetic-isotope effect to help corroborate the proposed mechanism. Density functional theory was employed at the B3PW91/6-31G(d',p') level to verify the Cl/CH(3) interchange mechanism and to characterize the interchange transition state. These calculations, which provide vibrational frequencies and moments of inertia of the molecule and transition state, were used to evaluate the statistical unimolecular rate constants. Matching the calculated and experimental rate constants, gave 62 ± 2 kcal mol(-1) as the threshold energy for interchange of the Cl atom and a methyl group. The calculated models also were used to reinterpret the thermal unimolecular reactions of neopentyl chloride and neopentyl bromide. The previously assumed Wagner-Meerwein rearrangement mechanism for these reactions can be replaced by a mechanism that involves the interchange of the halogen atom and a methyl group followed by HCl or HBr elimination from 2-chloro-2-methylbutane and 2-bromo-2-methylbutane. Electronic structure calculations also were done to find threshold energies for several related molecules, including 2-chloro-3,3-dimethylbutane, 1-chloro-2-methyl-2-phenylpropane, and 1-chloro-2-methyl-2-vinylpropane, to demonstrate the generality of the interchange reaction involving a methyl, or other hydrocarbon groups, and a chlorine atom. The interchange of a halogen atom and a methyl group located on adjacent carbon atoms can be viewed as an extension of the halogen atom interchange mechanisms that is common in 1,2-dihaloalkanes.
Lisowski
Carmen E
CE
Department of Chemistry, University of North Carolina-Asheville, One University Heights, Asheville, North Carolina 28804-8511, USA.
Duncan
Juliana R
JR
Ranieri
Anthony J
AJ
Heard
George L
GL
Setser
D W
DW
Holmes
Bert E
BE
D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D013237:Stereoisomerism
D006842:Hydrocarbons, Brominated; D006843:Hydrocarbons, Chlorinated; C554578:neopentyl chloride; C042053:neopentyl bromide