Correlation of Solvolysis Rates. IX. p-Methoxyneophyl Toluenesulfonate in a Variety of Solvents. Ionizing Power of Hydroxylic and Non-hydroxylic Solvents^1,2

Hydride transfer reactions. Oxidation of N-methylacridan by π acceptors

“…It is instructive to compare our solvent effects with those in the anchimerically-assisted ionization of p-methoxyneophyl p-toluenesulfonate at 75°C (k,,,) (33). Using the extensive comparisons of the common solvent polarity parameters published by Reichardt and Dimroth (34), we can estimate that [14] log k (1 + BQ, 25°C) % 0.58 log ki,, + constant The observation that log k for reaction of 1 with BQ is less sensitive to ion-solvating ability than log k,,, seems more consistent with partially developed charges in the rate-determining transition state (as in [12]) than with fully developed positive and negative charges (as in [13]).…”

The kinetics and mechanisms of organic reactions in liquid ammonia

“…For example, the rate of neighbouring group assisted solvolysis of 4-methoxyneophyl tosylate (I) is tremendously varied by about I 10 6 -fold on changing solvent from diethyl ether to formic acid due to the difficulty of solvating the leaving tosylate anion by ether. 27 Counter-ions can also affect the nucleophilicity of anionic nucleophiles, especially in non-polar solvents.…”

The Conversion of Meta- And Para-Substituted Benzaldoxime Arenesulfonates to Nitriles

“…A sample run is given in the Experimental section. (9), using the scale of solvent-ionizing power derived froin ionization of fi-methoxyneophyl fi-toluenesulfonate:…”

“…The a values for several rearrallgeinents have been calculated (9) from data available in the literature, being 0.690 for the ionic rearrangement of 9-decalyl perbenzoate; 0.569 for the allylic rearrangement of 1-phenylallyl 3,4,5-tribromobenzoate; and 0.119 for the Curtius rearrangement of benzoyl azide. In the latter, sensitivity to solvent change is low.…”