Arrhenius parameters for rearrangement of the neophyl, 1-indanylmethyl, 2-allylbenzyl, and 2-(2-vinylphenyl)ethyl radicals relative to hydrogen abstraction from tributylstannane
The temperature dependence of rates of several radical rearrangements relative to abstraction of hydrogen atom from tributylstannane has been determined. The rearrangement of 2-phenyl-2-methylpropyl to 1-phenyl-2-methylprop-2-yl (neophyl rearrangement) relative to hydrogen abstraction is represented by log (r/M) = (2.48 +/- 0.08) - (8.13 +/-0.16)/theta, theta = 2.3 RT kcal/mol. The rearrangement of 2-allylbenzyl to 2-indanylmethyl exhibited log (r/M) = (2.32 +/- 0.16)- (10.47 +/- 0.36/theta, and the rearrangement of 2-allylbenzyl to 2-tetralyl is represented by log (r/M) = (2.18 +/- 0.28) - (12.47 +/- 0.60)/theta. The rearrangement of 1-indanylmethyl to 2-tetralyl is represented by log (r/M) = (2.65 +/- 0.12) - (11.21 +/- 0.24)/theta. Closure of 2-(2-vinylphenyl)ethyl to the five-member ring occurs with a 7.3 +/- 0.6 kcal/mol barrier and was preferred over closure to the six-member ring by 2.1 +/- 1 kcal/mol. From known or estimated rates of abstraction of hydrogen from tributylstannane, rates of rearrangement of the radicals are estimated.
- Research Organization:
- Pacific Northwest Lab., Richland, WA
- OSTI ID:
- 6417876
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:14; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACTIVATION ENERGY
ARYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMATOGRAPHY
COMPLEXES
CORRELATIONS
DATA
DATA ANALYSIS
DECOMPOSITION
DEHYDROCYCLIZATION
ENERGY
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
INFORMATION
ISOMERIZATION
KINETICS
MASS SPECTRA
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TIN COMPLEXES