Mechanistic study on the oxidation of sulfacetamide by aqueous alkaline diperiodatoargentate(III)

Suresh D. Kulkarni, Praveen N. Naik, Sharanappa T. Nandibewoor

Research output: Contribution to journalArticle

Abstract

Oxidation of sulfacetamide (SUL), a sulfonamide drug by alkaline diperiodatoargentate(III) (DPA), a powerful oxidizing agent at 298 K and at a constant ionic strength of 0.50 mol/dm3, has been carried out spectrophotometrically at 360 nm. The results indicate that 3 mol of DPA consumed 1 mol of SUL (3:1). The oxidation product has been separated and characterized by IR and NMR spectral studies. The reaction is first order in [DPA] and has less than unit order in [SUL]. The rate constants increased with an increase in alkali concentration and decreased with increase in [IO 4-]. Ionic strength and dielectric constant of the medium had negligible effect on the reaction rate. A mechanism has been proposed which explains the observed orders and experimental observations. Monoperiodatoargentate(III) (MPA) has been considered as the active species for the title reaction. The reaction proceeds through a SUL:MPA complex which decomposes in a slow step to give the p-hydroxylamine benzenesulfonamide and Ag(I) species. Further oxidation in the subsequent fast steps yeilds nitroso and nitro derivative of benzenesulfonamide, each transformation consuming 1 mol of MPA. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The probable active species of oxidation have been identified.

Original languageEnglish
Pages (from-to)591-597
Number of pages7
JournalIndustrial and Engineering Chemistry Research
Volume48
Issue number2
DOIs
Publication statusPublished - 21-01-2009

Fingerprint

Sulfacetamide
Oxidation
Ionic strength
Rate constants
Hydroxylamine
Sulfonamides
Alkalies
Oxidants
Reaction rates
Permittivity
Chemical activation
Nuclear magnetic resonance
Thermodynamics
Derivatives
diperiodatoargentate(III)
Pharmaceutical Preparations

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Chemistry(all)
  • Industrial and Manufacturing Engineering

Cite this

@article{daa42406a2fa408a93f360f654aecac2,
title = "Mechanistic study on the oxidation of sulfacetamide by aqueous alkaline diperiodatoargentate(III)",
abstract = "Oxidation of sulfacetamide (SUL), a sulfonamide drug by alkaline diperiodatoargentate(III) (DPA), a powerful oxidizing agent at 298 K and at a constant ionic strength of 0.50 mol/dm3, has been carried out spectrophotometrically at 360 nm. The results indicate that 3 mol of DPA consumed 1 mol of SUL (3:1). The oxidation product has been separated and characterized by IR and NMR spectral studies. The reaction is first order in [DPA] and has less than unit order in [SUL]. The rate constants increased with an increase in alkali concentration and decreased with increase in [IO 4-]. Ionic strength and dielectric constant of the medium had negligible effect on the reaction rate. A mechanism has been proposed which explains the observed orders and experimental observations. Monoperiodatoargentate(III) (MPA) has been considered as the active species for the title reaction. The reaction proceeds through a SUL:MPA complex which decomposes in a slow step to give the p-hydroxylamine benzenesulfonamide and Ag(I) species. Further oxidation in the subsequent fast steps yeilds nitroso and nitro derivative of benzenesulfonamide, each transformation consuming 1 mol of MPA. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The probable active species of oxidation have been identified.",
author = "Kulkarni, {Suresh D.} and Naik, {Praveen N.} and Nandibewoor, {Sharanappa T.}",
year = "2009",
month = "1",
day = "21",
doi = "10.1021/ie8000474",
language = "English",
volume = "48",
pages = "591--597",
journal = "Industrial & Engineering Chemistry Product Research and Development",
issn = "0888-5885",
publisher = "American Chemical Society",
number = "2",

}

Mechanistic study on the oxidation of sulfacetamide by aqueous alkaline diperiodatoargentate(III). / Kulkarni, Suresh D.; Naik, Praveen N.; Nandibewoor, Sharanappa T.

In: Industrial and Engineering Chemistry Research, Vol. 48, No. 2, 21.01.2009, p. 591-597.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Mechanistic study on the oxidation of sulfacetamide by aqueous alkaline diperiodatoargentate(III)

AU - Kulkarni, Suresh D.

AU - Naik, Praveen N.

AU - Nandibewoor, Sharanappa T.

PY - 2009/1/21

Y1 - 2009/1/21

N2 - Oxidation of sulfacetamide (SUL), a sulfonamide drug by alkaline diperiodatoargentate(III) (DPA), a powerful oxidizing agent at 298 K and at a constant ionic strength of 0.50 mol/dm3, has been carried out spectrophotometrically at 360 nm. The results indicate that 3 mol of DPA consumed 1 mol of SUL (3:1). The oxidation product has been separated and characterized by IR and NMR spectral studies. The reaction is first order in [DPA] and has less than unit order in [SUL]. The rate constants increased with an increase in alkali concentration and decreased with increase in [IO 4-]. Ionic strength and dielectric constant of the medium had negligible effect on the reaction rate. A mechanism has been proposed which explains the observed orders and experimental observations. Monoperiodatoargentate(III) (MPA) has been considered as the active species for the title reaction. The reaction proceeds through a SUL:MPA complex which decomposes in a slow step to give the p-hydroxylamine benzenesulfonamide and Ag(I) species. Further oxidation in the subsequent fast steps yeilds nitroso and nitro derivative of benzenesulfonamide, each transformation consuming 1 mol of MPA. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The probable active species of oxidation have been identified.

AB - Oxidation of sulfacetamide (SUL), a sulfonamide drug by alkaline diperiodatoargentate(III) (DPA), a powerful oxidizing agent at 298 K and at a constant ionic strength of 0.50 mol/dm3, has been carried out spectrophotometrically at 360 nm. The results indicate that 3 mol of DPA consumed 1 mol of SUL (3:1). The oxidation product has been separated and characterized by IR and NMR spectral studies. The reaction is first order in [DPA] and has less than unit order in [SUL]. The rate constants increased with an increase in alkali concentration and decreased with increase in [IO 4-]. Ionic strength and dielectric constant of the medium had negligible effect on the reaction rate. A mechanism has been proposed which explains the observed orders and experimental observations. Monoperiodatoargentate(III) (MPA) has been considered as the active species for the title reaction. The reaction proceeds through a SUL:MPA complex which decomposes in a slow step to give the p-hydroxylamine benzenesulfonamide and Ag(I) species. Further oxidation in the subsequent fast steps yeilds nitroso and nitro derivative of benzenesulfonamide, each transformation consuming 1 mol of MPA. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The probable active species of oxidation have been identified.

UR - http://www.scopus.com/inward/record.url?scp=61649097314&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=61649097314&partnerID=8YFLogxK

U2 - 10.1021/ie8000474

DO - 10.1021/ie8000474

M3 - Article

VL - 48

SP - 591

EP - 597

JO - Industrial & Engineering Chemistry Product Research and Development

JF - Industrial & Engineering Chemistry Product Research and Development

SN - 0888-5885

IS - 2

ER -