Rate and Product Studies with 2-Methyl-2-Chloroadamantane under Solvolytic Conditions

Abstract

Reactions of 2-methyl-2-chloroadamantane (1) in a variety of pure and binary solvents have been studied at various temperatures and pressures up to 80 MPa. The sensitivity (m) to changes in solvent ionizing power of the Grunwald-Winstein equation, and the activation volume (∆V ‡ ) are calculated from the specific rates. An excellent linear relationship (R = 0.997) for 1, log (k/k0) = 0.80YCl + 0.11, and the activation volume,were observed. These values are similar to those for solvolyses of 1-adamantyl halides over the full range of solvents, suggesting that the unimolecular mechanism involving ion pairs is rate-determining. These observations are also compared with those previously reported for the corresponding 1-adamantyl derivatives and chloroformate esters.

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

“…Solvents were purified as described previously [26]. Kinetic measurements were made conductometrically using a rapid response technique [38]. Runs were carried out in duplicate with at least 70 readings taken at suitable intervals over approximately three half-lives and infinity readings were taken after ten half-lives.…”

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

“…The rate constants were obtained by averaging all of the values from, at least, duplicate runs. The products from the reactions of 1 under solvolytic conditions were analyzed after 10 half-lives by gas chromatography (GC-9A, Shimadzu, Kyoto, Japan) using a 2.1 m glass column containing 10% Carbowax 20M on Chromosorb WAW 80/100 as previously described [30]. The solvolysis products of 2 were also determined by GC/mass (Clarus 500 GC-Mass System, Perkin-Elmer, Ion mode EI, Waltham, MA, USA) analysis as described previously [3].…”