The kinetics of the reaction of cyclopentanol with PhNCO or OCN(Cd-In)NCO was studied in toluene, di-n-butyl ether and acetonitrile. The results suggest a predominant influence of the aggregation state of alcohol.
The dependence of the reaction rate of cyclopentanol with phenyl isocyanate on the concentration of monomeric alcohol [1] in toluene, di-n-butyl ether and acetonitrile suggests a reaction scheme involving various complexes.
In this paper, the kinetics of the reaction of phenylisocyanate with cyclopentanol, catalyzed by di(n-butyl)tin di-(2-ethylhexanoate) (DBTDEH), was studied at different temperatures in the same solvents as previously [1], i.e in acetonitrile (ACN), di-(n-butyl)ether (DBE) and toluene (Tol), in order to determine the Arrhenius energy, which is shown to be larger in the presence of the tin(IV) catalyst than in its absence [2], and the apparent activation entropy, which was derived from the values of the extrapolated intercepts of the In k-//7"graphs. The results demonstrate that entropic configurational effects are the prevailing cause of the accelerating effect of the tin(IV) catalyst on this reaction.
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