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Relative rates and arrhenius parameters for selected 1,2-arylmigrations and five- and six-member cyclizations

Technical Report ·
OSTI ID:5273091
; ;

The temperature dependent rates of radical rearrangements relative to abstraction of hydrogen atom from tri-n-butyltin hydride have been determined. The rearrangement of 2-phenyl-2-methylpropyl to 1-pheyl-2-methylpropyl (neophyl rearrangement) relative to hydrogen abstraction is represented by log r = 2.16 +- 0.08 - (7.48 +- 0.16)/THETA, THETA = 2.3RT kcal/mole. The rearrangement of o-allylbenzyl to 2-indanylmethyl exhibited log r = 2.24 +- 0.08 - (10.20 +- 0.25)/THETA, and the rearrangement of o-allylbenzyl to 2-tetralyl is represented by log r = (2.17 +- 0.13) - (12.32 +- 0.27)/THETA. The rearrangement of l-indanylmethyl to 2-tetralyl is represented by log r = 2.65 +- 0.06 - (11.21 +- 0.12)/THETA. The attempt to determine the cyclization rate of o-vinyl-2-phenylethyl radical to l-indanylmethyl and l-tetrlyl failed due to irreversible addition of tri-n-butyltin radical to the styrene double bond and other undefined competing reactions. However, kinetic closure to the five member ring was preferred over closure to the six member ring by roughly l kcal/mole. From known or estimated rates of abstract of hydrogen from tri-n-butyltin hydride, rates of rearrangement of the three radicals are derived.

Research Organization:
Pacific Northwest Lab., Richland, WA (USA)
DOE Contract Number:
AC06-76RL01830
OSTI ID:
5273091
Report Number(s):
PNL-SA-10946; ON: DE84005494
Country of Publication:
United States
Language:
English

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01 COAL, LIGNITE, AND PEAT
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AROMATICS
CHEMICAL REACTIONS
ISOMERIZATION
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
RESONANCE