The Kinetics of the Solvolysis of Acid Chlorides. III. The Influence of Solvent Composition on Reaction Rate, with Special Reference to the Solvolysis of Ethyl Chloroformate.

Solvolysis-decomposition ofN-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents

“…5 The alcoholyses of ethyl chloroformate are believed to involve a well defined bimolecular attack by the solvent and the entropies of activation are considerably more negative ( Ϫ 34·4 and Ϫ 33·7 eu). 23 While entropy of activation values must be interpreted with caution, the large variations observed for these systems are consistent with the other evidence presented, indicating that the alcoholyses of 1 proceed by an ionization mechanism with little, if any, nucleophilic solvation of the incipient cation at the transition state. Application of the one-term Grunwald-Winstein equation [equation (1) without the lN T term] to the 11 specific rates of solvolysis of 1 at 0·0 ЊC led to a plot with considerable dispersion for the different binary systems ( Figure 1) and a low correlation coefficient of 0·745.…”

Nucleophile Substitutionen an Kohlensäurederivaten. V. Kinetik und Mechanismus der Äthanolyse von Kohlensäure‐arylester‐chloriden

“…So wurde z. B. der gleiche Reaktionsmechanismus wie bei der Hydrolyse auch fur die Methanolyse und ,&thanolyse des Kohlensaure-athylester-chlorids gefunden [3].…”

Reaction Mechanism for the Hydrolysis of Titanium Alkoxides

“…In addition, Kivinen interpreted the reaction to proceed via a bimolecular path when the slopes of the straight line, n-value, were 2-3, while in the case of n-value of 6-7, the reaction occurred via a unimolecular path. 15 The plot of Kivinen's equation for the hydrolysis of Ti(OEt) 4 is shown in Figure 2. This plot gives straight lines at various temperatures and we can estimate that the hydrolysis of Ti(OEt) 4 obeys Kivinen's equation.…”