Kinetics and mechanism of oxidation of diethyl ketone by N-bromosuccinimide

Oxidative kinetics of diethyl ketone in perchloric acid media in the presence of mercuric acetate have been studied by using N-bromosuccinimide (NBS) as oxidant in the temperature range of 25°-50°C. It has been found that the order with respect to NBS is zero while with respect to diethyl ketone and [H⁺], it is unity. Succinimide, sodium perchlorate, and mercuric acetate have an insignificant effect on the reaction rate, while the dielectric effect was negative. A solvent isotope effect (k0_D2O/k0_H2O = 1.6–1.8) at 35°C has been observed. On the basis of the available evidences a suitable mechanism consistent with the experimental results has been proposed in which it is suggested that the mechanistic route for NBS oxidation in an acidic medium is through the enol form of the ketone. The magnitude of the solvent effect also supports the mechanism. Various activation parameters have been calculated, and the 1,2-dicarbonyl compound has been identified as the end product of the reaction.     

Kinetics and mechanism of the oxidation of primary alcohols by sodium N-chloroethylcarbamate

The oxidation of primary alcohols by sodium N-chloroethylcarbamate in acid solution, results in the formation of corresponding aldehydes. The reaction is first order with respect to the oxidant and alcohol. The rate increases with an increase in acidity. The oxidation of α,α-dideuterioethanol exhibited a primary kinetic isotope, k_H/k_D = 2.11 at 298 K. The value of solvent isotope effect k(H₂O)/k(D₂O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(OH)NHCl)⁺ has been postulated as the reactive species. Plots of (log k₂ + Ho) against (Ho + log[H⁺]) are linear with the slope, ?, having values from 1.78–1.87. This suggested a proton abstraction by water in the rate-determining step. The rates of oxidation of alcohols bearing both electron-withdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the C? H bond of the alcohol tothe oxidant and removal of a proton from the O? H group by a water molecule has 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.     

Oxidation of fluorenes by ammonium meta vanadate—a kinetic study

The oxidation of fluorene by vanadium(V) in aqueous acetic acid containing sulfuric acid (1.0M) at 50°C produces fluorenone and 2-hydroxy diphenyl 2′-carboxaldehyde. The order with respect to each reactant is found to be 1. The order dependence on sulfuric acid concentration is 4, indicating that V(OH)₂³⁺ could be the active species. An increase in the acetic acid percentage in the solvent medium increases the rate of the reaction. The effect of solvent variation has been discussed in the light of the acidity function and the polarity of the medium. The effect of substituents on the rate has been studied for seven substituted fluorenes, and a linear relationship exists between log k versus σ values with the slope ρ = -3.2. A small isotope effect is observed for the oxidation of the parent compound (k_H/k_D = 1.2). The effect of temperature on the rate of the reaction has been studied, and the activation parameters are discussed. A mechanism involving the rate-limiting formation of a cation-radical intermediate is proposed.     

Oxidation of naphthalene and phenanthrene by pyridinium fluorochromate (PFC)—a kinetic and mechanistic study

The kinetics of the oxidation of naphthalene and phenanthrene by pyridinium fluorochromate, C₅H₅NHCrO₃F, PFC, has been studied. The main product of the oxidation is the corresponding quinone. While each oxidation, studied in aqueous acetic acid (80–95%, v/v) medium, is first order with respect to the oxidant, the rate is almost independent of the substrate concentration. The reactions are catalyzed by acid, the acid-catalyzed reactions being very fast, which precluded determination of their order in acid medium. The kinetic isotope effect, k_H/k_D is 5.50 at 303 K for naphthalene. The reaction does not induce polymerization of acrylonitrile. The effects of temperature and solvent compositions were studied and activation parameters evaluated. Probable mechanisms are discussed.     

Kinetics and mechanism of the oxidation of diols by pyridinium bromochromate

The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid dependence has the form: k_obs=a+b[H⁺]. The oxidation of [1,1,2,2-²H₄]ethanediol exhibited a primary kinetic isotope effect (k_H/k _D=6.70 at 298 K). The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285–290, 1998.     

Kinetics and mechanism of oxidation of neutral α ‐amino acids by sodium N‐chloro‐p‐toluenesulfonamide in acid medium

Kinetics of oxidation of α ‐amino acids, glycine, valine, alanine, and phenylalanine, by sodium N‐chloro‐p‐toluenesulfonamide or chloramine‐T (CAT) has been investigated in HClO₄ medium at 30°C. The rate shows first‐order dependence on both CAT and amino acid concentrations and an inverse first‐order on [H⁺]. The variation of ionic strength and the addition of p‐toluenesulfonamide and Cl^? ion had no effect on the reaction rate. Decrease of dielectric constant of the medium by increasing the MeOH content decreased the rate. Rate studies in D₂O medium showed the inverse solvent‐isotope effect of k_D2O/k_H2O=0.50. Proton‐inventory studies were carried out using H₂O–D₂O mixtures. The activation parameters have been computed. The proposed mechanism and the derived rate law are consistent with the observed kinetic data. An isokinetic relationship is observed with β=323 K, indicating enthalpy as a controlling factor. The rate of oxidation increases in the following order: Gly < Val < Phe < Ala. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 49–55, 2002     

Kinetics and mechanism of the oxidation of aliphatic aldehydes by tetrabutylammonium tribromide

The oxidation of six aliphatic aldehydes by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid resulted in the formation of corresponding carboxylic acids. The reaction is first order with respect to TBATB and the aldehydes. The oxidation of deuteriated acetaldehyde (MeCDO) showed the presence of substantial kinetic isotope effect (k_H/k_D = 5.92 at 298 K). Addition of tetrabutylammonium chloride has no effect on the reaction rate. Tribromide ion has been proposed as the reactive oxidizing species. The rate constants correlate well with Taft's σ* values, the reaction constant being negative. A mechanism involving a hydride‐ion transfer from the aldehyde hydrate to the oxidant in the rate‐determining step has been suggested. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 390–395, 2001     

Studies on the kinetics of imidazolium fluorochromate oxidation of some meta‐ and para‐substituted anilines in nonaqueous media

The imidazolium fluorochromate (IFC) oxidation of meta‐ and para‐substituted anilines, in seven organic solvents, in the presence of p‐toluenesulfonic acid (TsOH) is first order in IFC and TsOH and is zero order with respect to substrate. The IFC oxidation of 15 meta‐ and para‐substituted anilines at 299–322 K complies with the isokinetic relationship but not to any of the linear free energy relationships; the isokinetic temperature lies within the experimental range. The specific rate of oxidizing species‐anilines reaction (k₂) correlates with substituent constants affording negative reaction constants. The rate data failed to correlate with macroscopic solvent parameters such as ε_r and E^N_T. A correlation of rate data with Kamlet–Taft solvatochromic parameters (α, β, π*) suggests that the specific solute–solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute–solvent complexation. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 166–175, 2006     

Oxidation of ethanolamines by sodium N‐bromobenzenesulfonamide in alkaline buffer medium: A kinetic and mechanistic study

The kinetics of oxidation of ethanolamines, monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA), by sodium N‐bromobenzenesulfonamide or bromamine‐B (BAB) in alkaline buffer medium (pH 8.7–12.2) has been studied at 40°C. The three reactions follow identical kinetics with first‐order in [oxidant] and fractional‐order each in [substrate] and [OH^?]. Under comparable experimental conditions, the rate of oxidation increases in the order: DEA > TEA > MEA. The added reaction product, benzenesulfonamide, retards the reaction rate. The addition of halide ions and the variation of ionic strength of the medium have no significant effect on the rate. The dielectric effect is negative. The solvent isotope effect k′(H₂O)/k′(D₂O) ≈ 0.92. Activation parameters for the composite reaction and for the rate‐limiting step were computed from the Eyring plots. Michaelis‐Menten type of kinetics is observed. The formation and decomposition constants of ethanolamine‐BAB complexes are evaluated. An isokinetic relationship is observed with β = 430 K indicating that enthalpy factors control the rate. For each substrate, a mechanism consistent with the kinetic data has been proposed. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 480–490, 2001     

Kinetics and mechanism of the oxidation of aliphatic alcohols by quinolinium fluorochromate

The oxidation of some aliphatic alcohols by quinolinium fluorochromate (QFC) in dimethyl sulfoxide leads to the formation of corresponding carbonyl compounds. The reaction is first order with respect to QFC. The reaction exhibited Michaelis‐Menten type kinetics with respect to the alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen‐ion dependence has the form: k_obs=a + b[H⁺]. The oxidation of [1,1‐²H₂]ethanol (MeCD₂OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analyzed using Taft's and Swain's multiparametric equations. The rate of disproportionation of the complex is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 469–475, 1999     

Linear free‐energy relationships in chromium(VI) oxidation of substituted benzylamines in nonaqueous media

The kinetics of oxidation of 11 para‐ and meta‐substituted benzylamines by imidazolium fluorochromate (IFC) in different organic solvent media has been investigated in the presence of p‐toluenesulfonic acid (TsOH). The reaction was run under pseudo‐first‐order conditions. The rate of the reaction was found to be first order in IFC and found to increase with increase in [TsOH]. Solution IR studies in combination with kinetic measurements were used to get a better insight into the mechanism of the oxidation process. The product analysis was carried out using GC–MS. Various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of the isokinetic relationship. The specific rate of oxidizing species benzylamines reaction (k₂) correlates with Hammett's substituent constants affording positive reaction constants. The rate data failed to correlate with macroscopic solvent parameters, such as ε_r and E^N_T, while showing satisfactory correlation with Kamlet–Taft's solvatochromic parameters (α, β, and π*) which suggests that the specific solute–solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute–solvent complexation. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 362–369, 2007     

Kinetics and mechanism of oxidation of dimethyl sulfoxide by chloramine-T in aqueous solution

The kinetics of oxidation of dimethyl sulfoxide (DMSO) by chloramine-T (CAT) is studied in HClO₄ and NaOH media with OsO₄ as a catalyst in the latter medium. In acid medium, the rate law is -d [CAT]/dt = k [CAT][DMSO][H⁺]. Alkali retards the reaction and the rate law takes the form -d [CAT]/dt = k [CAT][DMSO][OsO₄]/[NaOH], but is reduced to -d [CAT]/dt = k [CAT][DMSO] at higher alkali concentrations. The reaction is subjected to changes in (a) ionic strength, (b) concentrations of added neutral salts, (c) concentrations of added reaction product, (d) dielectric constant, and (e) solvent isotope effect, and the subsequent effects on the reaction rate are studied. The reaction mechanism in acid medium assumes an electrophilic attack by the free acid RNHCl (CAT′) at the sulfur site in DMSO, forming a reaction intermediate which subsequently decomposes to dimethyl sulfone on hydrolysis. Formation of a cyclic complex between RNHCl and OsO₄ which interacts with the substrate in a slow step explains the observed results in alkaline medium. The simplification of the rate equation at higher alkali concentrations is attributed to a direct reaction between chloramine-T and the substrate.     

Kinetics and mechanism of the oxidation of substituted benzaldehydes by hexamethylenetetramine‐bromine

The oxidation of thirty‐six monosubstituted benzaldehydes by hexa‐methylenetetramine‐bromine (HABR), in aqueous acetic acid solution, leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to HABR. Michaelis‐Menten–type kinetics were observed with respect to aldehyde. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of hexamethylenetetramine on the reaction rate. The oxidation of [²H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The effect of solvent composition indicated that the reaction rate increases with an increase in the polarity of the solvent. The rates of oxidation of meta‐ and para‐substituted benzaldehydes showed excellent correlations in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho‐substituted benzaldehydes correlated well with tetraparametric LDRS equation. The oxidation of para‐substituted benzaldehydes is more susceptible to the delocalization effect but the oxidation of ortho‐ and meta‐substituted compounds displayed a greater dependence on the field effect. The positive value of γ suggests the presence of an electron‐deficient reaction center in the rate‐determining step. The reaction is subjected to steric acceleration when ortho‐substituents are present. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 615–622, 2000     

Kinetics and mechanism of oxidation of chloramphenicol by 1-chlorobenzotriazole in acidic medium

Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO₄ medium over the temperature range 293–323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]_o and zero-order with respect to [CAP]_o. The fractional-order dependence of rate on [H⁺] suggests complex formation between CBT and H⁺. It fails to induce polymerization of acrylonitrile under the experimental conditions employed. Activation parameters are evaluated. The observed solvent isotope effect indicates the absence of hydride transfer during oxidation. Effects of dielectric constant and ionic strength of the medium on the reaction rate have been studied. Oxidation products are identified. A suitable reaction scheme is proposed and an appropriate rate law is deduced to account for the observed kinetic data.     

Kinetics and mechanism of oxidation of some para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B(CAB)

The kinetics of oxidation of ethyl S-phenylmercapto acetate and several para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B have been studied in 50% (V/V) aqueous ethanol medium containing phosphate buffer. This oxidation is of first order with respect to substrate and zero order with respect to oxidant. A catalytic effect of mercury is observed and the order with respect to mercury is fractional (0.74). The increase in pH decreases the rate of oxidation and the order with respect to H⁺ is 0.05. In general electron-releasing substituents accelerate the rate while electron-attracting groups retard the rate. A good correlation is found to exist between log k ₁ and Hammett constants. Susceptibility of the reaction to the steric effect of ortho-substituents has been analyzed in the light of application of Taft's steric energy parameters. © John Wiley & Sons, Inc.     

Kinetics of oxidation of benzyl alcohol by sodium N-chloro-p-toluenesulfonamide

The kinetics of oxidation of benzyl alcohol and substituted benzyl alcohols by sodium N-chloro-p-toluenesulfonamide (chloramine-T, CAT) in HClO₄ (0.1–1 mol/dm³) containing Cl^? ions, over the temperature range of 30–50°C have been studied. The reaction is of first order each with respect to alcohol and oxidant. The fractional order dependence of the rate on the concentrations of H⁺ and Cl^? suggests a complex formation between RNCl^? and HCl. In higher acidic chloride solution the rate of reaction is proportional to the concentrations of both H⁺ and Cl^7hyphen;. The observed solvent isotope effect (k/k) is 1.43 at 30°C. The reaction constant (p = ?1.66) and thermodynamic parameters are evaluated. Rate expressions and probable mechanisms for the observed kinetics have been suggested.     

Kinetics of oxidation of pantothenic acid by chloramine‐T in perchloric acid and in alkaline medium catalyzed by OsO4: A mechanistic approach

Kinetics of oxidation of pantothenic acid (PA) by sodium N‐chloro‐p‐toluenesulfonamide or chloramine‐T (CAT) in the presence of HClO₄ and NaOH (catalyzed by OsO₄) has been investigated at 313 K. The stoichiometry and oxidation products are same in both media; however, their kinetic patterns were found to be different. In acid medium, the rate shows first‐order dependence on [CAT]_o, fractional‐order dependence on [PA]_o, and inverse fractional‐order on [H⁺]. In alkaline medium, the rate shows first‐order dependence each on [CAT]_o and [PA]_o and fractional‐order dependence on each of [OH^?] and [OsO₄]. Effects of added p‐toluenesulfonamide and halide ions, varying ionic strength, and dielectric constant of medium as well as solvent isotope on the rate of reaction have been investigated. Activation parameters were evaluated, and the reaction constants involved in the mechanisms have been computed. The proposed mechanisms and the derived rate laws are consistent with the observed kinetics. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 201–210, 2005     

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 oxidation of aspirin by bromamine-T,N-bromosuccinimide,and N-bromophthalimide

The kinetics of the oxidation of aspirin (ASP) by bromamine-T (BAT), N-bromosuccinimide (NBS), and N-bromophthalimide (NBP) has been studied in aqueous perchloric acid at 303 K. The oxidation reaction follows identical kinetics with first-order in [oxidant], fractional-order in [ASP], and inverse fractional-order in [H⁺]. Under identical experimental conditions the extent of oxidation with different oxidizing agents is in the order: NBS>BAT>NBP. The rate decreased with decreasing dielectric constant of the medium. The variation of ionic strength and the addition of the reaction products and halide ions had no significant effect on the reaction rate. The solvent isotope effect was studied using D₂O. Kinetic parameters were evaluated by studying the reaction at different temperatures. The reaction products were identified by GC–MS. The proposed reaction mechanism and the derived rate law are consistent with the observed kinetic data. Formation and decomposition constants for ASP-oxidant complexes have been evaluated. Decarboxylation, bromination, and loss of acetic acid gave 2,4,6-tribromophenol. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 407–414, 1998