13153-76-9Relevant articles and documents
An examination of β-enolization in benzobicyclo[2.2.2], [3.2.1], and [3.2.2] ketones
Muir,Stothers
, p. 1290 - 1296 (2007/10/02)
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Photolytic Cleavage of Remote Functional Groups in Polyfunctional Molecules. Photolysis of exo- and endo-Benzobicycloocten-2-yl Chloride
Morrison, Harry,Muthuramu, Kayambu,Pandey, Genesh,Severance, Daniel,Bigot, Bernard
, p. 3358 - 3363 (2007/10/02)
The aryl-induced photolytic cleavage of a remote C-Cl bond, earlier reported for the 2-position in the benzonorbornenyl series, is extended to the 2-position of the title compounds (exo-BBCl and endo-BBCl).Cleavage with 254-nm excitation is an efficient reaction (ψdis = 0.45 and 0.005, exo and endo, respectively), involving the aryl singlet excited state.Radical and carbocation derived products are observed (eq.3), with the latter including an olefin (8), a cyclopropane (9), and rearranged ethers (10 and 13) attributed to "hot" cation intermediates.The rate constants for C-Cl cleavage sre as follows: exo 1.1*109 s-1; exo 2.2.2>, 3.8*108 s-1; endo , 1.7*106 s-1; endo , 2.7*105 s-1.These rates are discussed within the context of previously proposed mechanisms.