Kinetics and mechanism of the oxidation of amino acids by peroxomonosulphate oxidation of β-phenylalanine,isoleucine and threonine

The kinetics of oxidation of amino acids (AA) by peroxomonosulphate (PMS) in the presence and absence of formaldehyde were studied. Analysis of the results shows that the rate can be represented as, at constant [H⁺]and in the absence of formaldehyde

In the presence of formaldehyde and at constant [H⁺]the rate law is

Perusal of the kinetic results show that the formaldehyde catalysed reaction occurs $\text{\$}\text{?}$10⁵ times faster than uncatalysed and this is attributed to the formation of Schiff base. Mechanism of the reaction is discussed in terms of kinetic results.     

Kinetics of oxidation of ketoglutaric acids by alkaline chloramine-t solution

Kinetics of the oxidation of α-ketoglutaric and β-ketoglutaric acids by chloramine-T (CAT) have been investigated in highly alkaline media. The reactions show first order dependence in chloramine-T and fractional order in substrates. The order in hydroxide ions has been found to be second but shows a slight decrease at high concentration of alkali. No effect of p-toluene-sulphonamide was evident. Observed stoichiometry, positive effects of ionic strength and dielectric constant point to a mechanism involving formation of an intermediate in a termolecular rate determining slowest step among hypochlorite ion, hydroxide ion and enolic anion of keto acids followed by a fast step leading to products. Activation parameters have been computed and formaldehyde and formic acid were Identified as end-products.     

Kinetics and mechanism of the oxidation of substituted mandelic acids by acid permanganate

The oxidation of mandelic acid and nine monosubstituted mandelic acids by acid permanganate, in the presence of fluoride ions, have been studied. The reaction is of first order with respect to each the oxidant, the substrate and hydrogen ions. The kinetic isotope effect, k_H/k_D = 3·76 at 25°. The oxidation exhibits a reaction constant ?+= ?2·23 ± 0·07 at 25°. The oxidation does not induce polymerisation of acrylonitrile and does not show any solvent isotope effect. The activation enthalpies entropies are linearly related (r = 0·979). A mechanism involving transfer of a hydride ion to the oxidant is proposed.     

Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate

The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic isotope effect. Addition of benzyltrimethylammonium chloride enhances the rate. It is proposed that the reactive oxidizing species is [(PhCH₂Me₃N)⁺ (IZn₂Cl₆)^-]. Suitable mechanisms have been proposed.     

Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: k_obs =a +b[H⁺]. The oxidation of α-deuterioformic acid exhibits a substantial primary kinetic isotope effect (k_H/k_D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed.     

Kinetics and mechanism of the nitrosobenzene deoxygenation by trivalent phosphorous compounds

The reaction of aryl nitroso compounds with organic phosphines and phosphites in aerated media is a convenient non-photolytic procedure to generate aromatic nitroso oxides. The reaction rate constants and activation parameters of the key (for the proposed method of nitroso oxide generation) reaction of nitrosobenzene with tripenyl phosphite or para-substituted phosphines (4-RC₆H₄)₃P (R = MeO, Me, H, F), as well as that of para-methoxynitrosobenzene with triphenylphosphine in acetonitrile were determined by kinetic spectrophotometry and chemiluminescence. A significant transfer of the electron density to the nitroso compound occurs in the transition state of the reaction as was revealed using the Hammett correlation analysis and DFT calculations in the M06L/6-311+G(d,p) approximation. The introduction of the electron-donor substituent MeO into the para-position of PhNO decreases the reactivity of the nitroso compound by two orders of magnitude. The reactivity of triphenyl phosphite in the oxygen atom transfer reaction is lower by two orders of magnitude compared to that of triphenylphosphine. In the case of the reactions of PhNO with phosphines, the apparent rate constant depends on the oxygen content in the reaction medium.     

Kinetics of the chromic acid oxidation of glyoxylic and pyruvic acids

The reactions of glyoxylic and pyruvic acids by chromium (VI) have been studied in the presence of perchloric acid. Each reaction is first order with respect to chromium (VI), α-keto acid and hydrogen ion concentrations. The addition of sodium perchlorate to the reaction mixture had no effect on the rates but sodium chloride and sodium dihydrogen phosphate have retarding influences. Manganous ions increase the rate of reaction. The activation parameters are evaluated and tentative mechanisms for the oxidation reactions are discussed.     

Mechanism of iridium(III) catalysis in the oxidation of diols by N-bromoacetamide

Summary The kinetics of iridium(III)-catalysed oxidation of 1,2-ethanediol and 1,4-butanediol by N-bromoacetamide (NBA) in HClO₄ in the presence of [Hg(OAc)₂] as a scavenger for Br^– have been investigated. The reactions are zero-order with respect to both diols, and first-order in NBA at low NBA concentrations, tending to zero order at high concentrations. The order in Ir^III decreases from unity to zero at high iridium(III) concentrations. A positive effect on the oxidation rate is observed for [H⁺] and [Hg^II] whereas a negative effect is observed for acetamide and [Cl^–]. Ionic strength does not influence the oxidation rate. (H₂OBr)⁺ is postulated as the oxidizing species. A mechanism consistent with the observed kinetic data is proposed.     

Kinetics and mechanism of oxidation of S-phenylthioacetic acids by Ce(IV)

The kinetics of oxidation of several S-phenylthioacetic acids by ceric ammonium nitrate (CAN) in presence of perchloric acid has been studied spectrophoto- metrically in 50 %(v/v) aqueous acetic acid. The order with respect to Ce(IV) is one and the order with respect to S-phenylthioacetic acid is found to be 0.8. A linear plot of k_obs⁻¹ vs [substrate]⁻¹ with an intercept on the rate of axis suggests the formation of an equilibrium complex between the reactants prior to the rate determining step. The added acrylonitrile retards the reaction rate considerably suggesting that the oxidation process may involve a free radical mechanism. Electron-releasing substituents generally accelerate the rate, while electron-withdrawing groups retard the rate. A good correlation is found to exist between log k_1.8 and Hammett σ constants.     

Orthosilicate-mediated esterification of monosubstituted phosphinic acids

Monosubstituted phosphinic acids are esterified with orthosilicates in excellent yields. Phosphinylidene-containing acids react selectively under these conditions, while disubstituted phosphinic acids and phosphonic acids remain unchanged. One-pot procedures are also described for the preparation of phosphinate esters from an alcohol. This novel method provides a convenient and general alternative to more commonly employed conditions such as diazomethane or carbodiimide.     

C6, C7, and C8 perfluoroalkyl-substituted phosphinic acids

Reaction of red phosphorus with RfI in a 1:2 molar ratio at 230 degrees C led to the formation of a mixture of (Rf)2PI and (Rf)PI2 (Rf = C6F13, C7F15, C8F17) in about a 70:30 ratio, respectively. These mixtures were separated by vacuum distillation. (Rf)2PI (Rf = C6F13, C7F15) are yellow liquids whereas (C8F17)2PI is a yellow solid. Oxidation of (Rf)2PI with excess NO2 led to (Rf)2P(O)OH (Rf = C6F13, C7F15, C8F17) in > 90% isolated yields after aqueous hydrolysis of the anhydride intermediates. These highly fluorinated phosphinic acids are white solids with sharp melting points and are highly soluble in methyl sulfoxide (DMSO) and 1,1,2-trichlorotrifluoroethane. However, solubility in chloroform and methylene dichloride is low. These perfluoroalkylphosphinic acids were characterized by IR, NMR (1H, 19F, and 31P), and mass spectra and elemental analysis.     

Kinetics and mechanism of the oxidation of α-amino acids by n-bromoacetamide

The kinetics of the oxidation of eight α-amino adds by N-bromoacltanude have been studied in aqueous perchloric acid solution. The main products of the oxidation are the corresponding carbonyl compounds. The reaction is of first order with respect to the oxidant and the amino acid. The rate of oxidation decreases linearly with an increase in hydrogen ion concentration. The rate is decreased by the addition of acetamide. The oxidation of deuteriated glycine indicated the absence of a primary kinetic isotope effect. The reaction rate has been determined at different temperatures and activation parameters have been calculated. Hypobromous add has been postulated as the reactive oxidizing species. A rate-determining reaction of the neutral amino add and hypobromous add to give an N-bromo derivative has been proposed. The slow step is followed by a fast decomposition of the N-bromo derivative to yield the ultimate product.     

Crystal packing of ammonium salts of arylenebis(phenylphosphinic) acids

It was shown for the first time that the crystal packing mode of the ammonium salt of thiophene-2,5-diylbis(phenylphosphinic acid) substantially differs from that of the dimethyl-ammonium salt of 1,4-phenylenebis(phenylphosphinic acid). The former crystal packing is a three-layer supramolecular sandwich structure consisting of two anionic layers separated by a layer of ammonium cations, whereas the supramolecular organization of the latter salt is based on alternating layers of anions and cations linked by hydrogen bonds.     

Kinetics and mechanism of the oxidation of some neutralized α-Hydroxy acids by hexachloroiridate(IV)

Summary The kinetics of oxidation of some neutralized -hydroxy acids such as lactic (LA), mandelic (MA), -hydroxyisobutyric (IB) and benzilic (BA) acid by hexachloroiridate(IV) have been studied. The oxidation products are acetaldehyde, benzaldehyde, acetone and benzophenone for the respective reactions, which are first order with respect to each substrate and to iridium(IV). The reaction rate increases with increase in pH and salt concentrations. The temperature influence is quite marked in all these reactions. A mechanism involving the formation of an unstable complex, which decomposesvia a free radical pathway to give the respective reaction products, is proposed.     

T3P-assisted esterification and amidation of phosphinic acids

A few phosphinic acids, such as phenylphosphinic acids, 1-hydroxy-3-phospholene 1-oxides and 1-hydroxyphospholane oxides are esterified with simple alcohols in the presence of propylphosphonic anhydride (T3P^®). If 1.1 equiv of the T3P^® reagent is used, the esterifications are fast and efficient at 25° C. In the case of more reactive models it was enough to apply 0.66 equiv of T3P^® at 85° C under microwave conditions. The amidation of 1-hydroxy-3-methyl-3-phospholene oxide could also be accomplished under similar conditions.