Kinetics and mechanisms of solvolysis of 3-chloro-3-ethylpentane in alcohols as solvents.: Application of multiparametric equations and factor analysis to the solvolytic reactions of tert-alkyl halides

This paper introduces a new set of rate constants for solvolysis of 3-chloro-3-ethylpentane in eight monoalcohols, from methanol to 2-methylbutan-1-ol, and in 10 dialcohols, from ethane-1,2-diol to pentane-1,5-diol, and also in diethylene and triethylene glycol. These results together with previous obtained data for several solvolytic reactions of tert-alkyl halides (2-iodo-2-methylpropane, 2-bromo-2-methylpropane, 2-chloro-2-methylpropane, 2-bromo-2-methylbutane, 2-chloro-2-methylbutane and 3-chloro-3-methylpentane) in the same mono- and dialcohols were studied by means of a standard multiparametric approach and by target factor analysis (TFA). TFA provides an open criterion for selecting the quantity and nature of the possible causes of the variation in the rate constants. The results allow one to identify and quantify the dominant solute-solvent interaction mechanisms affecting the reactions. Solvent dipolarity, polarizability and hydrogen bond donor acidity are the main influences on reactivity, although mono- and dialcohols behave differently. Copyright (C) 2001 John Wiley & Sons, Ltd.