24309-43-1Relevant articles and documents
Hahn,Rothman
, p. 2409 (1969)
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Scully,F. et al.
, p. 5100 - 5102 (1973)
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Goldschmidt,Z.,Gutman,U.
, p. 3327 - 3331 (1974)
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Rosenthal,Winstein
, p. 2683 (1970)
Photolytic Cleavage of Remote Functional Groups in Polyfunctional Molecules. Activation of a γ C-Cl Bond in the endo- and exo-Benzobicycloocten-3-yl Chlorides
Morrison, Harry,Muthuramu, Kayambu,Severance, Daniel
, p. 4681 - 4687 (2007/10/02)
The aryl-induced photolytic cleavage of a distal C-Cl bond, earlier reported for a β-substituent benzobicyclo (eq 1) and - (eq 2) substrates, has been extended to the γ position in the title compounds (endo-BBOC and exo-BBOC).Photolyses of these compounds in methanolic solution using 254-nm light primarily lead to products derived from carbocation intermediates (eq 4 and 5) with quantum efficiencies for loss of starting material φdis = 8.1 * 10-2 and 7.6 * 10-3 (endo and exo, respectively).The greater reactivity of the endo isomer contrasts with that observed in the and series where large exo/endo rate ratios are the rule (Table III).This inverted reactivity pattern is attributed to the favorable aryl/chlorine relationship in the endo isomer (Figure 1), which compensates for the increased Ar-C3 separation otherwise characteristic of these γ functionalities.
