Sodium N-chlorobenzenesulfonamide Research Articles

Reaction 5-(Arylmethylidene)-2,4,6-pyrimidine-2,4,6(1H,3H,5H)-triones with Arenecarbaldehyde Phenylhydrazones in the Presence of Sodium N-Chlorobenzenesulfonamide

The reactions of 5-(arylmethylidene)-2,4,6-pyrimidine-2,4,6(1H,3H,5H)-triones with arenecarbaldehyde phenylhydrazones in the presence of sodium N-chlorobenzenesulfonamide give 2,3,7,9-tetraasaspiro-[4.5]dec-1-ene-6,8,10-triones in yields of 30–45%.

Conversion of imidazoles to imidazolones with chloramine-B: kinetic and mechanistic study

Oxidative conversion of 1H-imidazole (IzlH) and 2-substituted imidazoles viz., 2-ethyl-1H-imidazole (2-EtIzlH), 2-methyl-1H-imidazole (2-MeIzlH), 1H-imidazole-2-ester (2-EsIzlH), and 1H-imidazole-2-carbaldehyde (2-CaIzlH) to the corresponding imidazolones with sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) were established. This reaction was kinetically investigated at 303 K in HClO4 medium. Under comparable experimental conditions, the oxidation reactions followed identical kinetics for all the five imidazoles with a first-order dependence of rate on [CAB]o and fractional-order dependence each on [imidazole]o and [H+]. Effects of added benzenesulfonamide, halide ions, NaClO4, and MeOH on the rate of reaction have been studied. Reaction products were identified and characterized by GC–MS and NMR spectral analysis. The rates are measured at different temperatures and the composite activation parameters have been computed from the Arrhenius plots. Isokinetic temperature (β) was found to be 449 K which is higher than the experimental temperature (303 K), indicating that the rate has been under enthalpy control. Relative reactivity of these imidazoles is in the order: 2-EtIzlH > 2-MeIzlH > IzlH > 2-EsIzlH > 2-CaIzlH. H2O+Cl have been postulated as the reactive oxidizing species. The reaction mechanism and the derived rate law are in good agreement with the observed experimental results. Spectroscopic studies have been made for an intermediate complex formation between CAB and imidazole. Advantages of the present method include: mild reaction conditions, cost-effectiveness, short reaction time, ease of isolation of products, and the use of eco-friendly reagents. Hence, the methodology developed could be adopted for the facile oxidative conversion of imidazoles to imidazolones and can be scaled up to industrial operation with suitable modification.

RuCl3 Catalyzed and Uncatalyzed Oxidative Decolorization of Acid Orange 7 Dye with Chloramine-B in Acid Medium: Spectrophotometric, Kinetic and Mechanistic Study

Acid orange 7, chemically known as sodium 4-[(2E)-2-(2-oxonaphthalen-1-ylidene)hydrazinyl]benzenesulfonate, is extensively used for dyeing textiles, paper and leather. The discharge of wastewater containing this dye, causes environmental and health related problems. Therefore, in the present research, we have developed optimum conditions for the facile oxidative decolorization of this dye with sodium N-chlorobenzenesulfonamide or chloramine-B (CAB). The kinetics and mechanism of oxidative decolorization of acid orange 7 dye with CAB in acidic medium have also been studied spectrophotometrically at 303 K in the presence and absence of RuCl3 catalyst. Under similar experimental conditions, the reaction exhibits a first-order dependence of rate each on [CAB]o and [dye]o, and an inverse-fractional-order dependence on [H+] for both the RuCl3 catalyzed and uncatalyzed reactions. The order with respect to RuCl3 is fractional. Activation parameters have been computed. Dielectric effect is negative in both the cases. Oxidation products of the acid orange 7 dye are identified as 1,2-naphthoquinone and benzenesulfonic acid by GC–MS data. The RuCl3 catalyzed reaction is about four fold faster than the uncatalyzed reaction. The chemical oxygen demand value of the dye was determined. The mechanistic pathways and kinetic modelings have been computed based on experimental results. The developed oxidative decolorization method is expected to be helpful to treat acid orange 7 dye present in wastewater after suitable modifications. The stoichiometry of the reaction is in the mole ratio of 1:1(AO7:CAB) in both the cases as shown given below

Oxidation of Tetracaine Hydrochloride by Chloramine-B in Acid Medium: Kinetic Modeling

Tetracaine hydrochloride (TCH) is one of the potent local anaesthetics. A kinetic study of oxidation of tetracaine hydrochloride by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried in HClO4 medium at 303 K. The rate shows first-order dependence on [CAB]o, shows fractional–order dependence on [substrate]o, and is self-governing on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increased the rate. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction was found to be 1 : 5 and the oxidation products were identified by spectral analysis. The conjugate free acid C6H5SO2NHCl of CAB is postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

Kinetics and Mechanistic Chemistry of Oxidation of Butacaine Sulfate by Chloramine-B in Acid Medium

Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in HClO4 medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a firstorder dependence on both [CAB]o, and [substrate]o, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

Os(VIII)-Catalyzed Oxidation of Some Aliphatic Ketones by Sodium N-Chlorobenzenesulfonamide (Chloramine-B) in the Presence of Sodium Hydroxide: Kinetic Mechanistic Chemistry

Kinetics of oxidation of 2-propanone, 2-butanone, and 2-pentanone by chloramine-B (CAB) in presence of NaOH and OsO4 catalyst has been investigated at 303 K. The reaction rate shows a first–order dependence each on [CAB]o and [Os(VIII)], fractional-order on [NaOH], and zero-order on [ketone]o. The solvent isotope effect k/(H2O) / k/(D2O) = 0.58. Activation parameters have been deduced. An isokinetic relation is obtained with β = 340 K. The rate of oxidation of ketones follows the order: 2-pentanone > 2-butanone > 2-propanone. The Os(VIII) catalyzed reactions are 7 to 9 fold faster than the uncatalyzed reactions. Suitable mechanism and rate law have been proposed.

Mechanistic investigation of the oxidation of vitamin B1 with sodium N-chlorobenzenesulfonamide in presence of ruthenium(III) catalyst in hydrochloric acid medium: a kinetic approach

The oxidative cleavage of vitamin B1 (thiamine hydrochloride, THM) with sodium N-chlorobenzenesulfonamide (chloramine-B, CAB) has been kinetically investigated in HCl medium in presence of ruthenium(III) catalyst at 308 K. The oxidation reaction follows the rate law, −d[CAB]/dt = k [CAB] [Ru(III)] [H+] [THM]a [Cl−]b, where a and b are less than unity. Variation of ionic strength of the medium and addition of the reaction product, benzenesulfonamide (BSA) had no significant effect on the reaction rate. The change in relative permittivity of the medium affected by changing the solvent composition with acetonitrile has been studied. The stoichiometry of the reaction was found to be 1:1, and N-[(4-amino-2-methylpyrimidine-5-yl)methyl]benzensulfonamide and 2-(4-methylthiazol-5-yl)ethanol were identified as the oxidation products of vitamin B1. The reaction constants involved in the mechanism were computed. The reaction was studied at different temperatures and the overall activation parameters have been evaluated. C6H5SO2NHCl has been postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanisms and the relative rate laws have been deduced.

Ruthenium(III) – catalyzed oxidative cleavage of p-aminoazobenzene by chloramine-B in alkaline medium and uncatalyzed reaction in acid medium: spectrophotometric kinetic and mechanistic study

p-Aminoazobenzene (PAAB) is one of the important monoazo dyes and its oxidation kinetic study is of much use in understanding the mechanistic profile of PAAB in redox reactions. Consequently, the kinetics of oxidation of PAAB by sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) in HClO4 medium and in NaOH medium catalyzed by ruthenium(III) chloride (RuIII) have been investigated at 298 K. U.v.–vis spectrophotometry was used as a basic analytical approach in this study. Under an identical set of experimental conditions, the reactions of PAAB–CAB in HClO4 medium were facile, but the reactions became too slow to be studied in alkaline medium and hence ruthenium(III) chloride has been used as a catalyst in alkaline medium. The stoichiometry (1:2) and oxidation products (nitrosobenzene and p-nitrosoaniline) are the same in both media, but the kinetic and mechanistic patterns were found to be different. The experimental rate laws obtained are: − d[CAB]/dt = k [CAB]0 [PAAB]0 [H+] in acid medium and − d[CAB]0/dt = k [CAB]0 [PAAB]0[OH−]x[RuIII]y in alkaline medium, where x and y are less than unity. The reaction was examined with reference to changes in (a) concentration of benzenesulfonamide, (b) concentration of added neutral salts, (c) ionic strength, (d) dielectric permitivity and (e) solvent isotope effect. The reaction was also studied at different temperatures and the overall activation parameters have been evaluated. The oxidation reaction fails to induce the polymerization of added acrylonitrile. C6H4SO2NHCl and C6H4SO2NCl− have been postulated as the reactive oxidizing species in acidic and alkaline media, respectively. It was found that the reactions are nearly 20 times faster in acid medium in comparison with alkaline medium. It was also observed that ruthenium(III) was an efficient catalyst for the facile oxidation of PAAB by CAB in alkaline medium by making the reaction go twelve-fold faster than the uncatalyzed reactions. The catalytic constant (KC) has been calculated at different temperatures and the values of activation parameters with respect to ruthenium(III) have also been evaluated in alkaline medium. The observed results have been explained by plausible mechanisms and the relative rate laws have been deduced.

Mechanistic investigations of oxidation of isatins by sodium N-chlorobenzenesulfonamide in alkaline medium: A kinetic study

Abstract Oxidation of isatins (isatin, 5-methylisatin, 5-bromoisatin and 5-nitroisatin) to their anthranilic acids was performed efficiently with sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) in alkaline medium at 35±0.1°C. The reactions follow identical kinetics for all the isatins, being first-order dependence each in [CAB]o and [Isatin]o and inverse fractional-order on [NaOH]. Addition of halide ions and benzenesulfonamide, reduction product of CAB, do not significantly affect the rate. Variation of ionic strength of the medium had no effect on the rate, while the dielectric effect is negative. The solvent isotope effect was studied using D2O. Activation parameters for the overall reaction have been computed. The rates satisfactorily correlate with the Hammett σ relationship and the reaction constant ρ is −0.31 signifies that electron releasing groups accelerate the reaction while the electron withdrawing groups retard the rate. Values of ΔH≠ and ΔS≠ are linearly related and an isokinetic relationship is observed with β=376 K, indicating the reaction is controlled by enthalpy. The stoichiometry of the title reaction is found to be 1∶1. Oxidation products of isatins were identified as their corresponding anthranilic acids and the yields were found to be around 90 %. The observed results have been explained by a plausible mechanism and the related rate law deduced. This method offers several advantages including high yield of the products, short reaction times, easier isolation of products, and stable, cost effective and relatively non-toxic reagents, which make the reaction process simple and smooth.

Palladium(II)-Catalyzed Oxidation of α-Hydroxy Acids with Sodium N-Chlorobenzenesulfonamide in Perchloric Acid Solution: A Kinetic and Mechanistic Study

Kinetics of oxidation of glycolic acid (GA), lactic acid (LA) and 2-hydroxybutanoic acid (BA) with Chloramines B (CAB) catalyzed by Pd(II) in a HClO4 solution has been studied at 30 °C. The reaction rate shows first-order dependence each on [CAB], [hydroxy acid] and [Pd(II)] and a fractional-order dependence on [H+]. Additions of chloride ions, perchlorate ions and the reduction product of CAB, benzenesulfonamide (BSA), have no effect on the reaction rate. Variations of ionic strength and dielectric permittivity of the medium have no effect on the rate. Activation parameters have been evaluated. A mechanism consistent with kinetic data is proposed. A Taft linear free-energy relationship is observed for the reaction with ρ* = -3.593, indicating an increase in the rate with the presence of electron-donating substituents. An isokinetic relationship is observed with β = 376 K, indicating the effect of enthalpy factors on the rate.

Oxidation of aliphatic am ides by N-chlorobenzenesulfonamide in acid medium catalyzed by ruthenium(III) : a kinetic and mechanistic study

The kinetics of the ruthenium(III)-catalyzed oxidation of urea and substituted ureas, namely, methylurea, ethylurea and propylurea by sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) in HCI medium have been studied at 30°. The reaction rate shows a first order dependence each on CAB, amide and RuIII and fractional order on H+. Additions of halide ions and the reaction product of CAB (benzenesulfonamide) and the variation of ionic strength and dielectric constant of the medium do not have any significant effect on the reaction rate. Activation parameters have been evaluated. The rate increases in D2O medium. Proton inventory studies were made in H2O-D2O mixtures for both the amides. A Taft linear free energy relationship is observed for the reaction with I�* = -0.88 and -3.20 and I´ = -0.33, indicating that electron-donating groups enhance the rate. An isokinetic relation is observed with I² = 372 K confirmed by the Exner criterion. The protonation constant of monochloramine-B has been evaluated to be 8.6. A mechanism consistent with the observed kinetic data has been proposed. The rate of oxidation increases in the order: propylurea > ethylurea > methylurea > urea.

Sodium N-Chlorobenzenesulfonamide as a Selective Oxidant for Hexosamines in Alkaline Medium: A Kinetic and Mechanistic Study.

Oxidation of D-mannosamine (1), D-glucosamine (2), and D-galctosamine (3) by sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) at 313 K is followed by a shortening of carbon chain and obeys the rate law, rate = k[CAB][sugar][HO(-)](x)(), where x is less than unity. The products are arabinonic acid, ribonic acid, and erythronic acid for 1 and 2 with smaller amounts of glyceric and hexonic acids, while lyxonic and threonic acids are predominant in the oxidation of 3 with smaller amounts of glyceric and hexonic acids. Proton inventory studies made in a H(2)O-D(2)O mixture point toward a single transition state. In the proposed mechanism the alkoxy anion (S(-)) of the hexosamine formed in a base-catalyzed reaction at C-1 carbon is subjected to an electrophilic rate-limiting attack by Cl(+) of the oxidant. The hexonic acid formed is decarboxylated with loss of ammonia to form the respective pentose, which is further converted into the corresponding pentonic acid. The breaking of the bond between C-1 and C-2 carbons in pentose yields tetronic acids. The thermodynamic parameters for sugar alkoxy anion formation and activation parameters for the rate-limiting step have been evaluated.

Sodium N-chlorobenzenesulfonamide as an analytical reagent: Determination of amino acids and their metal complexes

Simple, elegant, and reproducible back-titration methods for the determination of arginine, histidine, threonine, glutamine, alanine, lysine, glycine, and serine in free state and in Zn, Cd, Ni, Cu, Ba, Sr, Mn, and Ag metal complexes with chloramine-B have been developed. The oxidation reaction involves a four-electron change per mole of amino acid, but a six-electron change is noticed with glycine and serine in various solvent and buffer media. The proposed analytical procedures for the assay of amino acids are useful for computing the number of amino acid ligands present in the respective metal complexes. The aromatic sulfonyl haloamine used, CAB, was prepared and then characterized by 1H and 13C FT-NMR spectral data.

Kinetics and mechanism of oxidation of allyl and crotyl alcohols by sodium N-chlorobenzenesulphonamide in hydrochloric acid medium

CHYBI ABSTRAKT !!!!

Some analytical applications of aromatic sulfonyl haloamines: Estimation of indigocarmine by chloramine-B, bromamine-T, and dibromamine-T

Sodium N-chlorobenzenesulfonamide (chloramine-B, CAB), sodium N-bromo- p-toluenesulfonamide (bromamine-T, BAT) and N,N′-dibromo- p-toluenesulfonamide (dibromamine-T, DBT) are employed as analytical reagents for estimating indigocarmine (IC) in solution. A four-electron stoichiometry is observed within 30 min in the following media: CAB, 0.1–1.0 N HCl or H 2SO 4 and pH 1 buffer; BAT, 0.01–0.10 N NaOH; DBT, glacial acetic acid. The back titration methods are fairly rapid, simple, and accurate. The product of oxidation, isatinsulfonate, was estimated by spectrophotometric measurements at 410 nm. The sulfonamides formed by reduction of the haloamines are detected by TLC and paper chromatography.

ChemInform Abstract: KINETICS AND MECHANISM OF THE OXIDATION OF SUBSTITUTED BENZYL ALCOHOLS BY SODIUM N‐CHLOROBENZENESULFONAMIDE

Chemischer InformationsdienstVolume 11, Issue 26 Preparative Organic Chemistry ChemInform Abstract: KINETICS AND MECHANISM OF THE OXIDATION OF SUBSTITUTED BENZYL ALCOHOLS BY SODIUM N-CHLOROBENZENESULFONAMIDE J. MUKHERJEE, J. MUKHERJEESearch for more papers by this authorK. K. BANERJI, K. K. BANERJISearch for more papers by this author J. MUKHERJEE, J. MUKHERJEESearch for more papers by this authorK. K. BANERJI, K. K. BANERJISearch for more papers by this author First published: July 1, 1980 https://doi.org/10.1002/chin.198026112AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume11, Issue26July 1, 1980 RelatedInformation

THE DECOMPOSITION OF SODIUM N-CHLOROBENZENESULFONAMIDE (CHLORAMINE-B)

Abstract The decomposition pressure of the hydrate of sodium N-chlorobenzenesulfonamide has been measured from 25° to 77°. Thermal analysis show that the compound undergoes two transitions accompanied by a mass loss each time. The first transition occurs at 80° to 125° and is endothermic, whereas the second one, at 188°, is exothermic. The thermal decomposition of the chloramine salt leads to the formation of sodium chloride, benzenesulfonamide, chlorobenzenesulfonamide, diphenyl sulfone, nitrogen and sulfur dioxide.