Epoxidation of Styrenes by Hydrogen Peroxide As Catalyzed by Methylrhenium Trioxide

Abstract

Methylrhenium trioxide, CH{sub 3}ReO{sub 3}, catalyzes the oxidation of styrenes by hydrogen peroxide. Kinetic studies by three methods were carried out in acidic CH{sub 3}CN/H{sub 2}O (1:1 v/v) solutions. The catalytically-active species are the mono-peroxide, CH{sub 3}Rc(O){sub 2}(O{sub 2}), A, and the bis-peroxide, CH{sub 3}Re(O)(O{sub 2}){sub 2}, B, which epoxidize a given styrene at a similar rate. The rate constants are relatively insensitive to steric hindrance, but increase with the nucleophilicity of the styrene, electron-donating groups on the olefinic carbons or on the aromatic ring enhancing the rate. The rate constants for meta- and para-substituted styrenes follow a linear Hammett relationship; correlation with {sigma}{sup +} gave {rho} = -0.93 {+-} 0.05. In CD{sub 3}CN, epoxides were observed by {sup 1}H NMR spectroscopy. cis-{beta}-Methylstyrene and trans-{beta}-methylstyrene led to the cis epoxide and the trans epoxide, respectively. In acidic CH{sub 3}CN/H{sub 2}O, the major products were 1,2-diols. In some cases C-C bond cleavage products were also observed, the extreme case being {beta}-methoxystyrene where the C-C bond was completely cleaved to yield benzaldehyde, formaldehyde, and methanol. 32 refs., 7 figs., 2 tabs.