Collect. Czech. Chem. Commun. 2007, 72, 1025-1036

Kinetics and Mechanism of Acid Catalysed Hydration of α-Methylstyrenes

Oldřich Pytelaa,* and Bronislav Trlidab

a Faculty of Chemical Technology, University of Pardubice, Čs. Legií 565, CZ-532 10 Pardubice, Czech Republic
b VUOS a.s. Research Institute for Organic Syntheses, Rybitví 296, CZ-532 18 Pardubice 20, Czech Republic


Twelve para-substituted α-methylstyrenes with substituents H, CH3, CF3, CH3O, CH3S, F, Cl, Br, CH3CO, CH3SO2, CN a NO2 were synthesised; additionally, the acid catalysed hydration kinetics of these compounds were measured in sulfuric acid in a concentration range c from 0.017 to 9.58 mol l-1, at 25.0 °C. The observed rate constants obtained were used to construct the kinetic acidity function and calculate the catalytic rate constants. Based on the evaluation of the acidity function kinetic dependence on acid medium concentration, and the substituent effects of acid catalysed hydration of α-methylstyrenes on the catalytic rate constants, the mechanism of acid catalysed hydration was verified. The mechanism involves the addition of a proton to the double bond of α-methylstyrene in the rate-limiting reaction step denoted as A-SE2. No evident difference was found between the effects of the acid medium on the acid catalysed hydration of styrenes and α-methylstyrenes, which indicates very similar activity coefficients of the reactants, and of the transition state of both substrates. The substituent effects evaluation shows that the rate-limiting step of the reaction consists in the addition of a proton to the substrate. The carbocation formation in the transition state of this reaction step proceeds roughly half-way compared with the extent of the carbocation formation by cumyl chloride hydrolysis. The obtained carbocation is in particular stabilised by the substituents with +M effect, while the influence of the substituents with -M and I effects is significantly smaller.

Keywords: Styrenes; Kinetics; Mechanism; Substituent effects; Kinetic acidity functions; Hammett equation; Carbocations.

References: 43 live references.