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Insight into D-galactose Oxidation: Kinetic and Mechanistic Analysis with Imidazolium Fluorochromate

Year 2024, Volume: 11 Issue: 2, 673 - 682, 15.05.2024
https://doi.org/10.18596/jotcsa.1387416

Abstract

In a 50% (v/v) aqueous acetic acid medium, a study on the oxidation kinetics of D-galactose by imidazolium fluorochromate (IFC) was conducted. The study revealed unit-order dependence on [D-galactose], [IFC], and [perchloric Acid]. The reaction was catalyzed by perchloric acid, and followed a 1:1 stoichiometric ratio. Adding sodium hyperchlorate (VII) salt did not affect the reaction. Polymerization of acrylonitrile was not observed in the oxidation process. The oxidation rates were retarded on adding Mn2+ ions in the mixture, and rates increased as the reaction medium’s dielectric constant (D) decreased. The observed results follow the Amis and Kirkwood plots {log k1 vs. (1/D) and ((D-1/2D+1))}. Several thermodynamic variables were determined by analyzing the kinetic data across a temperature range. Arabinose and formic acid were formed as the products of the reaction. A mechanistic path involving the formation of an ester followed by hydride ion transfer was proposed.

References

  • 1. Saha R, Nandi R, Saha B. Sources and toxicity of hexavalent chromium. J Coord Chem. 2011 May 20;64(10):1782–806. Available from: <URL>
  • 2. Khan Z, Kabir-ud-din. Kinetics and mechanism of D-glucose by chromium(VI) in perchloric acid. Indian J Chem. 2000 May;39A:522–7. Available from: <URL>
  • 3. Ukhurebor KE, Aigbe UO, Onyancha RB, Nwankwo W, Osibote OA, Paumo HK, et al. Effect of hexavalent chromium on the environment and removal techniques: A review. J Environ Manage. 2021 Feb;280:111809. Available from: <URL>
  • 4. Piancatelli G, Scettri A, D’Auria M. Pyridinium Chlorochromate: A Versatile Oxidant in Organic Synthesis. Synthesis. 1982;1982(04):245–58. Available from: <URL>
  • 5. Singh JV. Tetraethylammonium Chlorochromate : A Novel Oxidant, Kinetic and Mechanistic Aspect. Acta Cienc Indica [Internet]. Available from: <URL>
  • 6. Singh J, Kad GL, Vig S, Sharma M, Chhabra BR. Selective oxidation of primary alcohols with quinolinium chlorochromate. Indian J Chem. 1997 Mar;36 B:272–4. Available from: <URL>
  • 7. Chaudhuri MK, Chettri SK, Lyndem S, Paul PC, Srinivas P. Quinolinium Fluorochromate (QFC), C9H7NH[CrO 3F]: An Improved Cr(VI)-Oxidant for Organic Substrates. Bull Chem Soc Jpn. 1994 Jul;67(7):1894–8. Available from: <URL>
  • 8. Bhattacharjee MN, Chaudhuri MK, Purkayastha S. Some aspects of pyridinium fluorochromate, C5H5NhCrO3F (pfc), oxidations. stoichiometry of oxidation of alcohols, evidence for oxygen transfer, and the identity of the reduced chromium species. Tetrahedron. 1987 Jan;43(22):5389–92. Available from: <URL>
  • 9. Ghammamy S, Mazareey M. Tributylammonium chlorochromate, (C4H9)3NH[CrO3Cl] (TriBACC): A new, mild and stable oxidant for organic substrates. J Serb Chem Soc. 2005;70(5):687–93. Available from: <URL>
  • 10. Singh JV, Awasthi A, Dipti, Tomar A, Singh D. Kinetics and Mechanism of Oxidation of Reducing Sugars: A Review. Asian J Chem. 2013;25(2):595–611. Available from: <URL>
  • 11. Reasons why galactose is good for you [Internet]. International Dairy Federation; Available from: <URL>
  • 12. Coelho AI, Berry GT, Rubio-Gozalbo ME. Galactose metabolism and health. Curr Opin Clin Nutr Metab Care. 2015 Jul;18(4):422–7. Available from: <URL>
  • 13. Schaafsma G. Lactose and lactose derivatives as bioactive ingredients in human nutrition. Int Dairy J. 2008 May;18(5):458–65. Available from: <URL>
  • 14. Waisbren SE, Potter NL, Gordon CM, Green RC, Greenstein P, Gubbels CS, et al. The adult galactosemic phenotype. J Inherit Metab Dis. 2012 Mar;35(2):279–86. Available from: <URL>
  • 15. Berry G. The rate of de novo galactose synthesis in patients with galactose-1-phosphate uridyltransferase deficiency. Mol Genet Metab. 2004 Jan;81(1):22–30. Available from: <URL>
  • 16. Tomar A, Singh JV. Imidazolium Fluorochromate: A Novel Chromium (Vi) Oxidant, Mechanistic and Synthetic Aspects. Int J Anal Exp Modal Anal. 2023 Jan;15(1):356–81. Available from: DOI
  • 17. Pandurangan A, Rajlcumar GA, Arabindoo B, Murugesan V. Imidazolium fluorochromate (IFC): A new, mild, stable and selective chromium(VI) oxidant. Indian J Chem. 1999 Jan;38B:99–100. Available from: <URL>
  • 18. Katre SD. Recent Advances in the Oxidation Reactions of Organic Compounds using Chromium (VI) Reagents. Res J Chem Environ. 2020 Jan;24(1):130–51. Available from: <URL>
  • 19. S. Chidan Kumar C, Chandraju S, Mythily R, Ahmad T, M. Made Gowda N. Extraction of Sugars from Black Gram Peels by Reversed-Phase Liquid Chromatography Systems and Identification by TLC and Mass Analysis. Adv Anal Chem Sci Acad Publ. 2012 Aug 9;2(4):32–6. Available from: <URL>
  • 20. Agarwal GL, Tiwari S. Kinetics and mechanism of the oxidation of d-mannose with pyridinium chlorochromate. React Kinet Catal Lett. 1993 Jun;49(2):361–7. Available from: <URL>
  • 21. Tomar A, Kumar A. Kinetic and Mechanistic Study of the Oxidation of D-mannose by Tetraethylammonium Chlorochromate in Aqueous Acetic Acid Medium. Asian J Chem. 2006;18(4):3073–80. Available from: <URL>
  • 22. Feigl F, Anger V. Spot Tests in Organic Analysis. 7th ed. Amsterdam: Elsevier Science; 2014. ISBN: 978-0-444-59797-7
  • 23. Mardhanpally AK, Kodali SB, Jakku NR, Kamatala CR, Yerraguntla RR. Potassium hydrogen sulfate mediated kinetics and mechanism of oxidation of certain polyols by Quinolinium bound Cr(VI) reagents. SN Appl Sci. 2020 Oct;2(10):1747. Available from: <URL>
  • 24. Laidler KJ, Meiser JH, Sanctuary BC. Physical chemistry. 4th ed. Boston: Houghton Mifflin; 2003. 1060 p. ISBN: 978-0-618-12341-4
  • 25. Espenson JH. Chemical kinetics and reaction mechanisms. 2nd ed. repr. New York [etc.]: McGraw-Hill Custom Publishing; 2007. ISBN: 978-0-07-288362-6
  • 26. Panday D, Jain H, Kalal R. Evaluation of kinetic parameters for oxidation of thioacids by benzimidazolium dichromate: A mechanistic study. J Indian Chem Soc. 2022 Apr;99(4):100390. Available from: <URL>
  • 27. Amis ES. Solvent effects on reaction rates and mechanisms: Tab. New York: Acad. Pr; 1967. 326 p. ISBN: 978-0-12-057350-9
  • 28. Kirkwood JG. Theory of Solutions of Molecules Containing Widely Separated Charges with Special Application to Zwitterions. J Chem Phys. 1934 Jul 1;2(7):351–61. Available from: <URL>
  • 29. Glasstone S, Laidler KJ, Eyring H. The Theory of Rate Processes. New York: McGraw-Hill; 1941. ISBN: 978-0-07-023360-7
  • 30. Arnaut L. Enzymatic catalysis. In: Chemical Kinetics [Internet]. Elsevier; 2021 [cited 2023 Nov 4]. p. 409–39. Available from: <URL> ISBN: 978-0-444-64039-0
  • 31. Mardhanpally AK, Kamatala CR, Pulusu V, Kodali SB, Jakku NR, Yerraguntla RR. Cornforth’s and Corey-Suggs Cr(VI) compounds as efficient reagents for selective oxidation of certain polyols in aqueous KHSO4 medium –A kinetic and mechanistic approach. Chem Data Collect. 2022 Jun;39:100847. Available from: <URL>
  • 32. Bruice PY. Organic chemistry. Eighth edition, global edition. Harlow: Pearson; 2017. 1336 p. ISBN: 978-1-292-16034-4
  • 33. Fadnis AG, Shrivastava SK. Kinetics of oxidation of aldoses by thallium(III) in acid perchlorate medium. Carbohydr Res. 1982 Apr;102(1):23–9. Available from: <URL>
  • 34. Saha B, Das M, Mohanty RK, Das AK. Micellar Effect on the Reaction of Chromium(VI) Oxidation of L-Sorbose in the Presence and Absence of Picolinic Acid in Aqueous Acid Media: A Kinetic Study. J Chin Chem Soc. 2004 Apr;51(2):399–408. Available from: <URL>
  • 35. Virtanen POI, Lindroos-Heinänen R. Comparison of the kinetics of oxidation of monosaccharides by Ce (IV), Cr (VI) and V (V). Acta Chem Scand. 1988 Jul 1;42:411–3. Available from: <URL>
  • 36. Sen Gupta KK, Nath Basu S, Sen Gupta S. Kinetics and mechanism of oxidation of d-fructose and l-sorbose by chromium(VI) and vanadium(V) in perchloric acid medium. Carbohydr Res. 1981 Nov;97(1):1–9. Available from: <URL>
  • 37. Rizzotto M, Frascaroli MI, Signorella S, Sala LF. Oxidation of l-rhamnose and d-mannose by chromium(VI) in aqueous acetic acid. Polyhedron. 1996 May;15(9):1517–23. Available from: <URL>
  • 38. Sala LF, Signorella SR, Rizzotto M, Frascaroli MI, Gandolfo F. Oxidation of L -rhamnose and D -mannose by Cr(VI) in perchloric acid. A comparative study. Can J Chem. 1992 Jul 1;70(7):2046–52. Available from: <URL>
  • 39. Daier V, Signorella S, Rizzotto M, Frascaroli MI, Palopoli C, Brondino C, et al. Kinetics and mechanism of the reduction of Cr VI to Cr III by D -ribose and 2-deoxy- D -ribose. Can J Chem. 1999 Jan 1;77(1):57–64. Available from: <URL>
  • 40. Sen Gupta KK, Basu SN. Kinetics and mechanism of oxidation of d-erythrose and dL-glyceraldehyde by chromium(VI) and vanadium(V) in perchloric acid medium. Carbohydr Res. 1980 Nov;86(1):7–16. Available from: <URL>
  • 41. Sengupta KK, Samanta T, Basu SN. Kinetics and mechanism of oxidation of ethanol, isopropanol and benzyl alcohol by chromium(VI) in perchloric acid medium. Tetrahedron. 1986 Jan;42(2):681–5. Available from: <URL>
  • 42. Kali Sen Gupta K, Dey S, Sen Gupta S, Adhikari M, Banerjee A. Evidence of esterification during the oxidation of some aromatic aldehydes by chromium (VI) in acid medium and the mechanism of the oxidation process. Tetrahedron. 1990 Jan;46(7):2431–44. Available from: <URL>
  • 43. Tomar A, Kumar A. Kinetics and mechanism of oxidation of D-fructose by tetraethylammonium chlorochromate in aqueous acetic acid. J Indian Chem Soc. 2006 Nov 30;83:1153–7. Available from: <URL>
Year 2024, Volume: 11 Issue: 2, 673 - 682, 15.05.2024
https://doi.org/10.18596/jotcsa.1387416

Abstract

References

  • 1. Saha R, Nandi R, Saha B. Sources and toxicity of hexavalent chromium. J Coord Chem. 2011 May 20;64(10):1782–806. Available from: <URL>
  • 2. Khan Z, Kabir-ud-din. Kinetics and mechanism of D-glucose by chromium(VI) in perchloric acid. Indian J Chem. 2000 May;39A:522–7. Available from: <URL>
  • 3. Ukhurebor KE, Aigbe UO, Onyancha RB, Nwankwo W, Osibote OA, Paumo HK, et al. Effect of hexavalent chromium on the environment and removal techniques: A review. J Environ Manage. 2021 Feb;280:111809. Available from: <URL>
  • 4. Piancatelli G, Scettri A, D’Auria M. Pyridinium Chlorochromate: A Versatile Oxidant in Organic Synthesis. Synthesis. 1982;1982(04):245–58. Available from: <URL>
  • 5. Singh JV. Tetraethylammonium Chlorochromate : A Novel Oxidant, Kinetic and Mechanistic Aspect. Acta Cienc Indica [Internet]. Available from: <URL>
  • 6. Singh J, Kad GL, Vig S, Sharma M, Chhabra BR. Selective oxidation of primary alcohols with quinolinium chlorochromate. Indian J Chem. 1997 Mar;36 B:272–4. Available from: <URL>
  • 7. Chaudhuri MK, Chettri SK, Lyndem S, Paul PC, Srinivas P. Quinolinium Fluorochromate (QFC), C9H7NH[CrO 3F]: An Improved Cr(VI)-Oxidant for Organic Substrates. Bull Chem Soc Jpn. 1994 Jul;67(7):1894–8. Available from: <URL>
  • 8. Bhattacharjee MN, Chaudhuri MK, Purkayastha S. Some aspects of pyridinium fluorochromate, C5H5NhCrO3F (pfc), oxidations. stoichiometry of oxidation of alcohols, evidence for oxygen transfer, and the identity of the reduced chromium species. Tetrahedron. 1987 Jan;43(22):5389–92. Available from: <URL>
  • 9. Ghammamy S, Mazareey M. Tributylammonium chlorochromate, (C4H9)3NH[CrO3Cl] (TriBACC): A new, mild and stable oxidant for organic substrates. J Serb Chem Soc. 2005;70(5):687–93. Available from: <URL>
  • 10. Singh JV, Awasthi A, Dipti, Tomar A, Singh D. Kinetics and Mechanism of Oxidation of Reducing Sugars: A Review. Asian J Chem. 2013;25(2):595–611. Available from: <URL>
  • 11. Reasons why galactose is good for you [Internet]. International Dairy Federation; Available from: <URL>
  • 12. Coelho AI, Berry GT, Rubio-Gozalbo ME. Galactose metabolism and health. Curr Opin Clin Nutr Metab Care. 2015 Jul;18(4):422–7. Available from: <URL>
  • 13. Schaafsma G. Lactose and lactose derivatives as bioactive ingredients in human nutrition. Int Dairy J. 2008 May;18(5):458–65. Available from: <URL>
  • 14. Waisbren SE, Potter NL, Gordon CM, Green RC, Greenstein P, Gubbels CS, et al. The adult galactosemic phenotype. J Inherit Metab Dis. 2012 Mar;35(2):279–86. Available from: <URL>
  • 15. Berry G. The rate of de novo galactose synthesis in patients with galactose-1-phosphate uridyltransferase deficiency. Mol Genet Metab. 2004 Jan;81(1):22–30. Available from: <URL>
  • 16. Tomar A, Singh JV. Imidazolium Fluorochromate: A Novel Chromium (Vi) Oxidant, Mechanistic and Synthetic Aspects. Int J Anal Exp Modal Anal. 2023 Jan;15(1):356–81. Available from: DOI
  • 17. Pandurangan A, Rajlcumar GA, Arabindoo B, Murugesan V. Imidazolium fluorochromate (IFC): A new, mild, stable and selective chromium(VI) oxidant. Indian J Chem. 1999 Jan;38B:99–100. Available from: <URL>
  • 18. Katre SD. Recent Advances in the Oxidation Reactions of Organic Compounds using Chromium (VI) Reagents. Res J Chem Environ. 2020 Jan;24(1):130–51. Available from: <URL>
  • 19. S. Chidan Kumar C, Chandraju S, Mythily R, Ahmad T, M. Made Gowda N. Extraction of Sugars from Black Gram Peels by Reversed-Phase Liquid Chromatography Systems and Identification by TLC and Mass Analysis. Adv Anal Chem Sci Acad Publ. 2012 Aug 9;2(4):32–6. Available from: <URL>
  • 20. Agarwal GL, Tiwari S. Kinetics and mechanism of the oxidation of d-mannose with pyridinium chlorochromate. React Kinet Catal Lett. 1993 Jun;49(2):361–7. Available from: <URL>
  • 21. Tomar A, Kumar A. Kinetic and Mechanistic Study of the Oxidation of D-mannose by Tetraethylammonium Chlorochromate in Aqueous Acetic Acid Medium. Asian J Chem. 2006;18(4):3073–80. Available from: <URL>
  • 22. Feigl F, Anger V. Spot Tests in Organic Analysis. 7th ed. Amsterdam: Elsevier Science; 2014. ISBN: 978-0-444-59797-7
  • 23. Mardhanpally AK, Kodali SB, Jakku NR, Kamatala CR, Yerraguntla RR. Potassium hydrogen sulfate mediated kinetics and mechanism of oxidation of certain polyols by Quinolinium bound Cr(VI) reagents. SN Appl Sci. 2020 Oct;2(10):1747. Available from: <URL>
  • 24. Laidler KJ, Meiser JH, Sanctuary BC. Physical chemistry. 4th ed. Boston: Houghton Mifflin; 2003. 1060 p. ISBN: 978-0-618-12341-4
  • 25. Espenson JH. Chemical kinetics and reaction mechanisms. 2nd ed. repr. New York [etc.]: McGraw-Hill Custom Publishing; 2007. ISBN: 978-0-07-288362-6
  • 26. Panday D, Jain H, Kalal R. Evaluation of kinetic parameters for oxidation of thioacids by benzimidazolium dichromate: A mechanistic study. J Indian Chem Soc. 2022 Apr;99(4):100390. Available from: <URL>
  • 27. Amis ES. Solvent effects on reaction rates and mechanisms: Tab. New York: Acad. Pr; 1967. 326 p. ISBN: 978-0-12-057350-9
  • 28. Kirkwood JG. Theory of Solutions of Molecules Containing Widely Separated Charges with Special Application to Zwitterions. J Chem Phys. 1934 Jul 1;2(7):351–61. Available from: <URL>
  • 29. Glasstone S, Laidler KJ, Eyring H. The Theory of Rate Processes. New York: McGraw-Hill; 1941. ISBN: 978-0-07-023360-7
  • 30. Arnaut L. Enzymatic catalysis. In: Chemical Kinetics [Internet]. Elsevier; 2021 [cited 2023 Nov 4]. p. 409–39. Available from: <URL> ISBN: 978-0-444-64039-0
  • 31. Mardhanpally AK, Kamatala CR, Pulusu V, Kodali SB, Jakku NR, Yerraguntla RR. Cornforth’s and Corey-Suggs Cr(VI) compounds as efficient reagents for selective oxidation of certain polyols in aqueous KHSO4 medium –A kinetic and mechanistic approach. Chem Data Collect. 2022 Jun;39:100847. Available from: <URL>
  • 32. Bruice PY. Organic chemistry. Eighth edition, global edition. Harlow: Pearson; 2017. 1336 p. ISBN: 978-1-292-16034-4
  • 33. Fadnis AG, Shrivastava SK. Kinetics of oxidation of aldoses by thallium(III) in acid perchlorate medium. Carbohydr Res. 1982 Apr;102(1):23–9. Available from: <URL>
  • 34. Saha B, Das M, Mohanty RK, Das AK. Micellar Effect on the Reaction of Chromium(VI) Oxidation of L-Sorbose in the Presence and Absence of Picolinic Acid in Aqueous Acid Media: A Kinetic Study. J Chin Chem Soc. 2004 Apr;51(2):399–408. Available from: <URL>
  • 35. Virtanen POI, Lindroos-Heinänen R. Comparison of the kinetics of oxidation of monosaccharides by Ce (IV), Cr (VI) and V (V). Acta Chem Scand. 1988 Jul 1;42:411–3. Available from: <URL>
  • 36. Sen Gupta KK, Nath Basu S, Sen Gupta S. Kinetics and mechanism of oxidation of d-fructose and l-sorbose by chromium(VI) and vanadium(V) in perchloric acid medium. Carbohydr Res. 1981 Nov;97(1):1–9. Available from: <URL>
  • 37. Rizzotto M, Frascaroli MI, Signorella S, Sala LF. Oxidation of l-rhamnose and d-mannose by chromium(VI) in aqueous acetic acid. Polyhedron. 1996 May;15(9):1517–23. Available from: <URL>
  • 38. Sala LF, Signorella SR, Rizzotto M, Frascaroli MI, Gandolfo F. Oxidation of L -rhamnose and D -mannose by Cr(VI) in perchloric acid. A comparative study. Can J Chem. 1992 Jul 1;70(7):2046–52. Available from: <URL>
  • 39. Daier V, Signorella S, Rizzotto M, Frascaroli MI, Palopoli C, Brondino C, et al. Kinetics and mechanism of the reduction of Cr VI to Cr III by D -ribose and 2-deoxy- D -ribose. Can J Chem. 1999 Jan 1;77(1):57–64. Available from: <URL>
  • 40. Sen Gupta KK, Basu SN. Kinetics and mechanism of oxidation of d-erythrose and dL-glyceraldehyde by chromium(VI) and vanadium(V) in perchloric acid medium. Carbohydr Res. 1980 Nov;86(1):7–16. Available from: <URL>
  • 41. Sengupta KK, Samanta T, Basu SN. Kinetics and mechanism of oxidation of ethanol, isopropanol and benzyl alcohol by chromium(VI) in perchloric acid medium. Tetrahedron. 1986 Jan;42(2):681–5. Available from: <URL>
  • 42. Kali Sen Gupta K, Dey S, Sen Gupta S, Adhikari M, Banerjee A. Evidence of esterification during the oxidation of some aromatic aldehydes by chromium (VI) in acid medium and the mechanism of the oxidation process. Tetrahedron. 1990 Jan;46(7):2431–44. Available from: <URL>
  • 43. Tomar A, Kumar A. Kinetics and mechanism of oxidation of D-fructose by tetraethylammonium chlorochromate in aqueous acetic acid. J Indian Chem Soc. 2006 Nov 30;83:1153–7. Available from: <URL>
There are 43 citations in total.

Details

Primary Language English
Subjects Reaction Kinetics and Dynamics
Journal Section RESEARCH ARTICLES
Authors

Ashish Tomar 0000-0002-1316-0359

Unik Arora 0009-0009-2099-3541

Jai Veer Singh 0009-0005-2695-6881

Publication Date May 15, 2024
Submission Date November 7, 2023
Acceptance Date February 2, 2024
Published in Issue Year 2024 Volume: 11 Issue: 2

Cite

Vancouver Tomar A, Arora U, Singh JV. Insight into D-galactose Oxidation: Kinetic and Mechanistic Analysis with Imidazolium Fluorochromate. JOTCSA. 2024;11(2):673-82.