Neighboring Group Participation by a Pyridine Ring. 2. Effects of Aromatic Substituents on Solvolysis of 5,8-Methano-5,6,7,8-tetrahydroisoquinoline and Benzonorbornene Derivatives

Article abstract of DOI:10.1021/jo00206a019

A series of 3-substituted 5,8-methano-5,6,7,8-tetrahydroisoquinolin-7-exo-ols (4) and 2-substituted benzonorbornen-6-exo-ols (5) were prepared and the hydrolysis rates of their arenesulfonates were determined in 50percent aqueous tert-butyl alcohol.The relative rates of CH3O, CH3, H, and Cl substituted derivatives at 50 deg C were 150, 7.39, 1, and 0.14 for the isoquinoline series and 130, 4.96, 1, and 0.15 for the benzo series, respectively.The products found were the corresponding alcohols with the retained configuration.The ρ-?⁺ plots for the rates yielded linearcorrelations with ρ values of -3.19 for the isoquinolines and -3.09 for the benzo series.The data indicate major participation by both aromatic rings.