Kinetic and Thermodynamic Effects in the Thermal Electrocyclic Ring-Openings of 3-Fluorocyclobutene, 3,3-Difluorocyclobutene, and 3-(Trifluoromethyl)Cyclobutene

Authors:

• William R. Dolbier,
• Thomas A. Gray,
• Jeffrey J. Keaffaber,
• Lech Paweł Celewicz,
• Henryk Koroniak

Abstract

The synthesis and thermal electrocyclic ring-opening of 3-fluorocyclobutane, 4,3,3-difluorocyclobutane, 5, and 3-(trifluoromethyl)cyclobutane, 6, are reported. Activation energies for their ring-openings were found to be 28.1, 45.0, and 36.3 kcal/mol, respectively. 6 was found to form both the (E)- and the (Z)-5,5,5-trifluoro- 1,3-butadienes, in a 95:5 ratio. Thermal equilibrations of the diene products from 4 and 6 were also carried out. The results demonstrate that a CF₃ group exhibits only a slight preference for outward rotation (ΔE_a = 1.2 kcal/mol), while a fluorine substituent gives rise to a much more dramatic outward rotational preference (ΔE_a = 13.8 kcal/mol). These results were consistent with those previously reported for perfluorinated systems and with theoretical expectations. © 1990, American Chemical Society. All rights reserved.