Kinetics for the reaction of a secondary alkyl radical with tri-n-butylgermanium hydride and calibration of a secondary alkyl radical clock reaction

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DOIResolve DOI: http://doi.org/10.1021/jo00392a003
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TypeArticle
Journal titleJournal of Organic Chemistry
ISSN0022-3263
Volume52
Issue16
Pages35093514; # of pages: 6
AbstractArrhenius parameters for the reaction of a secondary alkyl radical with tri-n-butylgermanium hydride have been measured by using the cyclization of 1-methyl-5-hexenyl radical as a "clock" reaction. At 298 K the rate constant is 1.8 × 10 4 M -1 s -1, which makes the secondary alkyl radical/n-Bu 3GeH reaction about 80 times slower than the corresponding reaction with tri-n-butyltin hydride. The secondary alkyl radical clock reaction has been rather precisely calibrated by using new data and data from the literature. An attempt to carry out similar experiments with 1,1-dimethyl-5-hexenyl yielded much less precise data for the cyclization of this tertiary alkyl radical. Reliable kinetic data for hydrogen abstraction from n-Bu 3GeH by tertiary alkyl radicals could not be obtained by using either the parent bromide or appropriate N-hydroxypyridine-2-thione esters as alkyl radical sources.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276752
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Record identifier830b1ef7-1c4b-415b-9ebe-f890b0b2b44b
Record created2015-10-13
Record modified2016-05-09
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