No abstract

Kinetics and mechanism of oxidation of substituted and unsubstituted 4-oxoacids (S) by N-bromosuccinimide (NBS) in aqueous acetic acid medium have been studied potentiometrically. The reaction follows first-order kinetics, each in 4-oxoacids, NBS and H + . The effect of changes in the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. Based on the kinetic results and the product analysis, a suitable mechanism has been proposed for the reaction of NBS with 4-oxoacids.

The inhibition of mineralization of urinary stone forming minerals by medicinal plantsi.e. Achyranthes asperaLinn,Passiflora leschenaultiiDC,Solena amplexicaulis(Lam.) Gandhi,Scoparia dulcisLinn andAerva lanata(Linn.) been investigated. The inhibition efficiency was studied. Increased intake of fruits juice and seed extract of our plants would be helpful in urinary stone prophylaxis.

The kinetics of oxidation of some essential amino acids namely, valine, leucine and phenylalanine, (AA) by N-chlorosaccharin (NCSA) in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H + ]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

The kinetics of oxidation of 3-benzoylpropionic acid (KA) withN-bromoacetamide (NBA) have been studied potentiometrically in 50:50 (v/v) aqueous acetic acid medium at 298 K The reaction was first order each with respect to [KA], [NBA] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of acetamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. A mechanism consistent with observed results have been proposed and the related rate law was deduced.