Solvolysis of 9-fluorenyl bromide and tosylate. Nucleophilic solvent intervention and insignificance of antiaromaticity

Solvolysis of benzylic chlorides with extended charge delocalization. ?-tert-butyl(2-naphthyl)methyl, 9-fluorenyl and monosubstituted benzhydryl chlorides

“…Extensive charge delocalization through the whole ring system and the presence of significant nucleophilic solvent intervention at the reaction center in the transition state are likely, as have been found in the solvolysis of 9-fluorenyl bromide. 30 On the other hand, the use of either N T or N OTs with Y xBnCl in equation (2) gave less satisfactory linear correlations (r = 0.97-0.98 in Table 7) for 3e. Regression analysis using N OTs and Y BnCl resulted in a linear relationship with r = 0.993.…”

“…12,14 Interesting results were also observed from the solvolysis of 9-fluorenyl chloride (2) and monosubstituted benzhydryl chlorides (3). Like the corresponding bromides, 14,18,30 good linear relationships could not be found for log k vs Y Cl [equation (1)], as was shown in Table 2. Deviations from linear correlations with Y BnCl were observed for 2,3a-c and 3e.…”

“…35 Our recent studies, however, indicated significant nucleophilic solvent intervention in the solvolysis of monosubstituted benzhydryl bromides containing a strong electron-withdrawing group, 14,18 and in the case of 9-fluorenyl bromide. 30 Moreover, a new Y xBnBr scale was found to be necessary to correlate the solvolytic reactivities of 2 and 3.…”

Solvent Effects on the Solvolysis of Some Secondary Tosylates. Applications of YBnOTs and YxBnOTs Scales to Mechanistic Studies

“…However, an excellent linear correlation with Y xBnOTs , R = 0.997 and m = 1.09, was resulted. Consequently, a similar delocalization of positive charge in fluorenyl cation (13) and 2-methylnaphthyl cation (14) at the transition state could be concluded. The apparent difference between Y xBnOTs and Y BnOTs is likely the consequence of the solvent interaction with different extent of positive charge delocalization, such as 14 and benzyl cation 15.…”

“…For tosylates of the extended benzylic system, 1-tertbutyl-1-(2-naphthyl)methyl tosylate (8) was proposed as the reference standard in the relevant study. 13,14 In this paper a complete scale of Y xBnOTs and the mechanistic application of Y BnOTs and Y xBnOTs are reported. Moreover, similar to the corresponding chlorides 15 and bromides, 10b solvent effects on the Hammett-type correlation will also be examined.…”