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Chemical effects of the (n,gamma) activation of bromine in the alkyl bromides. Isomerization in teh bromobutanes

Journal Article · · Journal of Physical Chemistry
DOI:https://doi.org/10.1021/j100837a503· OSTI ID:4172483

The four isomeric bromobutanes were irradiated with low neutron fluxes (total dose <200 r) in order to study carbon chain isomerization. All four isomers were found to undergo fragmentation to bromomethane, bromoethane, and bromopropanes to the extent of 4.5 to 6% of the radiobromime products. They also yield 10 to 20% high-boiling organic bromides, mostly dibroraobutanes. For three of the isomers, the organic retention of radiobromine is in the expected range of 30 to 40a; (CH3)3CBr gave nearly 100% organic retention. Carbon chain isomerization was present for all isomers, but it was highest for (CH3)3/CBr, 13.6% as 2-bromobutane. The unusual product proportions of (CH3)3CBr are explained by the formation of (CH3)3C c ations or radicals; this explanation is supported by the fact that the (CH3)3/ CBr ratio of radioactive 2-bromobutane to 2-bromo-2-methylpropane, 0.2, is close to the 0.23 ratio observed for the equilibration of n-butane with 2-methylpropane in the presence of AlBr3 at 25°C.

Research Organization:
Atomic Energy of Canada, Ltd., Chalk River, Ont.
Sponsoring Organization:
USDOE
NSA Number:
NSA-14-021509
OSTI ID:
4172483
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 8 Vol. 64; ISSN 0022-3654
Country of Publication:
Country unknown/Code not available
Language:
English

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