Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).
The title compound 1-exo (with minor amounts of its C8 epimer 1-endo) was prepared by Wolff-Kishner reduction of the cycloadduct of 1,3-cyclohexadiene and cyclopropylketene. The [1,3]-migration product 2-endo was synthesized by efficient selective cyclopropanation of endo-5-vinylbicyclo[2.2.2]oct-2-ene at the exocyclic π-bond. Gas phase thermal reactions of 1-exo afforded C8 epimerization to 1-endo, [1,3]- migrations to 2-exo and 2-endo, direct fragmentation to cyclohexadiene and vinylcyclopropane, and CPC rearrangement in the following relative kinetic order: kep > k13 > kf > kCPC.
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. phyllis.leber@fandm.edu.
Phyllis A
PA
Leber
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. ajn5014@psu.edu.
Anthony J
AJ
Nocket
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. william.hancock-cerutti@fandm.edu.
William
W
Hancock-Cerutti
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. christopher.bemis@fandm.edu.
Christopher Y
CY
Bemis
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. wintkhant.khine@fandm.edu.
Wint Khant
WK
Khine
Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA. joseph.mohrbacher@fandm.edu.
Joseph A
JA
Mohrbacher Iii
Department of Chemistry, Syracuse University, Syracuse, NY 13244-4100, USA. jbaldwin@syr.edu.
John E
JE
Baldwin
D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D053138:Cyclohexenes / Q000138:chemical synthesis / Q000737:chemistry*; D005740:Gases / Q000138:chemical synthesis / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D044367:Phase Transition
D001643:Bridged Bicyclo Compounds; D053138:Cyclohexenes; D005740:Gases; C000591852:exo-8-cyclopropyl-bicyclo(4.2.0)oct-2-ene; C034005:1,3-cyclohexadiene