Rate Constants and Arrhenius Functions for Ring Opening of a Cyclobutylcarbinyl Radical Clock and for Hydrogen Atom Transfer From the Et3B−MeOH Complex
- 15 May 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 73 (12), 4740-4742
- https://doi.org/10.1021/jo800500e
Abstract
Kinetics of ring opening of the 1-cyclobutyldodecyl radical (1) were studied, and an Arrhenius function over the temperature range -20 to 47 degrees C was determined. The radical clock reaction has kinetics described by log k = 13.2 - 13.5/2.313 RT (in kcal/mol), and k = 1.5 x 10(3) s(-1) at 20 degrees C. Previous kinetic studies of hydrogen atom transfer trapping of radical 1 by the triethylborane-methanol complex at variable temperatures (J. Org. Chem. 2007, 72, 5098) were analyzed with the newly obtained kinetic data.Keywords
This publication has 23 references indexed in Scilit:
- Adjusting the Top End of the Alkyl Radical Kinetic Scale. Laser Flash Photolysis Calibrations of Fast Radical Clocks and Rate Constants for Reactions of BenzeneselenolThe Journal of Organic Chemistry, 1999
- Hydrogen Donor Abilities of the Group 14 HydridesPublished by Elsevier BV ,1999
- Competition Methods and Scales for Alkyl Radical Reaction KineticsTetrahedron, 1993
- A convenient method for kinetic studies of fast radical rearrangements. Rate constants and Arrhenius function for the cyclopropylcarbinyl radical ring openingJournal of the American Chemical Society, 1989
- Rate constants and Arrhenius parameters for the reactions of primary, secondary, and tertiary alkyl radicals with tri-n-butyltin hydrideJournal of the American Chemical Society, 1981
- The ring-opening reactions of cyclobutylmethyl and cyclobutenylmethyl radicalsJournal of the Chemical Society, Perkin Transactions 2, 1981
- Free-radical clocksAccounts of Chemical Research, 1980
- The kinetics and mechanism of ring opening of radicals containing the cyclobutylcarbinyl systemJournal of the Chemical Society, Perkin Transactions 2, 1980
- Kinetic applications of electron paramagnetic resonance spectroscopy. 27. Isomerization of cyclopropylcarbinyl to allylcarbinylJournal of the American Chemical Society, 1976
- Cyclization of 5-hexenyl radicalsJournal of the American Chemical Society, 1972