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Isomerization of chemically activated bicyclo[3.1.0]hex‐2‐ene and related C 6 H 8 isomers
Author(s) -
Rose Timothy L.,
Seyse R. J.,
Crane P. M.
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060613
Subject(s) - chemistry , isomerization , ene reaction , cyclopentadiene , arrhenius equation , methylene , rrkm theory , bicyclic molecule , reaction rate constant , singlet state , photochemistry , benzene , medicinal chemistry , computational chemistry , kinetics , organic chemistry , activation energy , catalysis , physics , quantum mechanics , nuclear physics , excited state
Singlet methylene was reacted with cyclopentadiene to give chemically activated bicyclo[3.1.0]hex‐2‐ene (BCH). The rate of isomerization of BCH to 1,4‐cyclohexadiene, 1,3‐cyclohexadiene, cis ‐1,3,5‐hexatriene, and l‐methylcyclopentadiene is compared with calculated rate constants using the RRKM theory and measured or estimated thermal Arrhenius parameters. Subsequent isomerizations of the C 6 H 8 products are also measured and calculated. These include 1,4‐cyclohexadiene to benzene and the reversible reactions between 1,3‐cyclohexadiene, cis ‐1,3,5‐hexatriene, and trans ‐1,3,5‐hexatriene. The results provide new data for several of these reactions which have not been observed in thermal studies. Agreement between the observed and calculated rates using the strong collision assumption is satisfactory except for the trans ‐1,3,5‐hexatriene to cis ‐1,3,5‐hexatriene reaction.