No abstract

No abstract

No abstract

The kinetics of the permanganate oxidation of formic acid in aqueous perchloric acid a t 30°C were examined by the spectrophotometric method. The chemical reaction 2Mn0, A BHCOOH + 2H + -2Mn02 + 3C0, + 4H20. appears to proceed via several parallel reactions. The overall rate equation has been obtained by using statistical multilinear regression analysis of the 660 cases studied, and the presence in the rate equation of two new terms in relation to previous studies shows that both permanganate autocatalgtic effects and acid media inhibition must be taken into account when the reaction proceeds at constant ionic strength.

2LSChloranil and bromanil react with an excess of triphenylphosphoniocyclopentadienide to yield the 2 5and 2,6-disubstituted quinone derivatives through t w o parallel, second-order reactions. Kinetic data suggest that the reaction proceeds in t w o steps, involving addition to form a polar betaine intermediate followed b y elimination of hydrogen halide. The activation parameters strongly suggest that the loss of halide is of the E, type. The empirical rate law has been established carrying out a multi-response non-linear least-squares analysis followed b y a Gaussian de-convolution of the visible spectra of the reaction mixtures.The reaction of triarylphosphoniocyclopentadienides 1 with tetrahalo-p-benzoquinones 2 proceeds to give monosubstituted products 3 in virtually quantitative yield which have been characterized by UV spectroscropy (A = 700 nm), multinuclear NMR and X-ray ~rystallography.~-~ @+Ar,