Kinetics and Equilibrium Constants for Reactions of α-Phenyl-Substituted Cyclopropylcarbinyl Radicals
Abstract
Laser-flash photolysis methods were used to determine Arrhenius functions for cyclizations of the 4,4-diphenyl-3-butenyl (2) and trans-4-phenyl-3-butenyl (5) radicals to the 1,1-diphenylcyclopropylcarbinyl (1) and 1-phenylcyclopropylcarbinyl (4) radicals, respectively. At 20 °C, the cyclization rate constants are 1.7 × 10^7 and 5.4 × 10^6 s^(-1). Equilibrium constants for the two processes were estimated and evaluated with thermochemical data and via computational methods, and Arrhenius functions for the ring-opening reactions of the cyclopropylcarbinyl radicals were calculated. The cyclization reactions of 2 and 5 are strongly enthalpy controlled. Production of radicals 1 and 2 from the corresponding tert-butylperoxy esters in the presence of Et_3SnH gave diphenylcyclopropylmethane and 1,1-diphenyl-1-butene from H-atom trapping of radicals 1 and 2 and 4-phenyl-1,2-dihydronaphthalene which derives from the product radical formed by addition of the radical moiety in 2 to the cis-phenyl group. Rate constants for the latter cyclization of 2 and for reactions of radicals 1 and 2 with Et_3SnH were obtained from the indirect kinetic studies.
Additional Information
© 2000 American Chemical Society. Received April 8, 1999. Revised Manuscript Received February 2, 2000. Publication Date (Web): March 21, 2000. We are grateful to the National Science Foundation for financial support (CHE-9614968 to M.N. and GP-8540 to J.D.R.).Attached Files
Supplemental Material - ja991114h_s.pdf
Supplemental Material - ja991114h_sa.pdf
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Additional details
- Eprint ID
- 60659
- DOI
- 10.1021/ja991114h
- Resolver ID
- CaltechAUTHORS:20151001-101404659
- CHE-9614968
- NSF
- GP-8540
- NSF
- Created
-
2015-10-02Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field