On Attempts at Solvolytic Generation of Aryl Cations

The solvolysis of phenyl triflate (3), phenyl nonaflate (4), o-methylphenyl nonaflate ( 5 ) , o-cyclopropylphenyl nonaflate (6), o-methoxyphenyl triflate (7), 2,6-dimethoxyphenyl triflate (S), 2,6-diisopropylphenyl triflate (9), 3 3 dimethoxyphenyl triflate (lo), 3,5-dicyclopropylphenyl triflate (11), 3,5-di(2-methylcyclopropyl)phenyl triflate (12), 2,4,6-tricyclopropylphenyl triflate (13), and 2,4,6-triisopropylphenyl triflate (14) were examined in great detail under a wide variety of conditions. In highly polar nonnucleophilic solvents no reaction was observed and the unreacted triflates were recovered quantitatively. In the presence of nucleophiles or nucleophilic solvents the sole products observed were the corresponding phenols. Careful labeling and product studies showed that these phenols arose by nucleophilic attack on sulfur and S-0 bond cleavage. We have not been able to find any evidence for aryl cation intermediates,