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Year 2025, Volume: 9 Issue: 1, 53 - 62, 05.01.2025

Ketul Kumawat Anurag Choudhary , Om Prakash

https://doi.org/10.33435/tcandtc.1443581

Abstract

References

  • [1] E.J. Corey and W.J. Suggs, Pyridinium chlorochromate. An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds. Tetrahedron letters,, 16(31) (1975) 2647-2650.
  • [2] F.S. Guziec and F.A. Luzio, Synthesis, 9 (1975) 691-695.
  • [3] M.N. Bhattacharjee, M.K. Choudhuri, H.S. Dasgupta, N. Roy and D.R. Khathing, Synthesis, 7 (1982) 588-593.
  • [4] K. Balasubramanian and V. Prathiba, Indian J. Chem., 25B (1986) 326-331.
  • [5] A. Pandurangan, V. Murugesan and P. Palamichamy, J. Indian Chem. Soc., 72 (1995) 479-482.
  • [6] S. Mahajan, B. Sinhg, V.S. Jasrotia, M. Sharma, H.N. Sheikh and B.L. Kalsotra, Oxid. Commun.,31(2), 2008, 356-364
  • [7] D. Chandora, P. Bishnoi, G. Ram, O. Prakash and V. Sharma, Orient J. Chem.,37(6) (2021) 1329-1335.
  • [8] D. Yajurvedi, O. Prakash and A. Choudhary, 11(2) 2023, 57-68.
  • [9] D. Kumar, M. Baghmar and A. Choudhary, Res. J. Chem. Environ., 27(4) (2023) 101–106.
  • [10] R. Kalla, D. Kumar, A. Choudhary and V. Sharma, Oxidation kinetics and mechanistic studies of thioacids by imidazolium dichromate. Rasayan Journal of Chemistry14(4) (2021) 2436-2441.
  • [11] J. Kalpan, Deuterium Isotope Effects in the Bromine Oxidation of Ethanol and of Acetaldehyde1. Journal of the American Chemical Society, 80(11) (1958) 2639-2642.
  • [12] K.B. Wiberg, The deuterium isotope effect of some ionic reactions of benzaldehyde. Journal of the American Chemical Society 76 (1954) 5371-5375.
  • [13] H.C. Brown, G.C. Rao and S.U. Kulkarni, Stoichiometry of the oxidation of primary alcohols with pyridinium chlorochromate. Evidence for a two-electron change. The Journal of Organic Chemistry44 (1979) 2809-2810.
  • [14] M.N. Bhattacharjee, M.K. Choudhuri, S. Purakayastha, 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, 43(1987) 5389-5392.
  • [15] L. Liu and W.E. Guo, Isokinetic relationship, isoequilibrium relationship, and enthalpy− entropy compensation. Chemical reviews, 101(3) (2001) 673-696
  • [16] O. Exner, Prog. Phys. Org. Chem., 10 (1973) 411.
  • [17] M.J. Kamlet, J.L.M. Abboud, M.H. Abraham and R.W. Taft, Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters,. pi.*,. alpha., and. beta., and some methods for simplifying the generalized solvatochromic equation. The Journal of Organic Chemistry,48 (1983) 2877-2887.
  • [18] O. Exner, Additive physical properties. I. General relationships and problems of statistical nature. Collection of Czechoslovak Chemical Communications, 31 (1966) 3222-3251.
  • [19] C.G. Swain, M.S. Swain, A.L. Powel and S. Alunni, Antioxidant activity of phenols related to vitamin E. Are there chain-breaking antioxidants better than. alpha.-tocopherol?. Journal of the American Chemical Society, 105(3) (1983) 492-502.
  • [20] C.D. Johnson, The Hammett equation, University Press, Cambridge, (1973) 78.
  • [21] S.K. Dayal, S. Ehrenson and R.W. Taft, Substituent effects, electronic transmission, and structural dependence of. pi. delocalization as studied with the p-fluorophenyl tag. Journal of the American Chemical Society, 94(26) (1972) 9113-9122.
  • [22] C.G. Swain, S.H. Unger, N.R. Rosenquest and M.S. Swain, Substituent effects on chemical reactivity. Improved evaluation of field and resonance components. Journal of the American Chemical Society, 105(3) (1972) 492-502.
  • [23] M. Charton and B. Charton, Bull. Soc. Chim. Fr., (1988) 199-210 and references cited therein.
  • [24] M. Charton, Nature of the ortho effect. XI. Reaction rates of carboxylic acids with diazodiphenylmethane. The Journal of Organic Chemistry, 40(4) (1975) 407-411.
  • [25] E.S. Gould, Mechanism & structure in organic chemistry, Holt, Rinehart & Winston Inc., NY (1964).

CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE

Year 2025, Volume: 9 Issue: 1, 53 - 62, 05.01.2025

Ketul Kumawat Anurag Choudhary , Om Prakash

https://doi.org/10.33435/tcandtc.1443581

Abstract

The reaction of 2-picolinium chlorochromate (PICC) with thirty-six monosubstituted benzaldehydes in dimethylsulphoxide (DMSO) results in the production of the corresponding benzoic acids by oxidation. An enzymatic reaction exhibiting Michaelis-Menten kinetics was observed in relation to the reactants. The process is facilitated by hydrogen ions; the hydrogen ion dependency is expressed as kobs= a + b [H+]. The oxidation of deuterated benzaldehyde (PhCDO) showed a significant main kinetic isotope impact. The reaction was examined in nineteen distinct organic solvents, and the influence of the solvent was analyzed using Taft's and Swain's multi-parametric equations. The oxidation rates of benzaldehydes with para and meta substitutions exhibited a strong association using Charton's tri-parametric LDR equation. On the other hand, the oxidation of benzaldehydes with ortho substitutions showed a good correlation using the tetra-parametric LDRS equation. The oxidation of benzaldehydes with para-substituents is more influenced by the delocalized effect compared to the oxidation of compounds with ortho- and meta-substituents, which show a stronger reliance on the field effect. The occurrence of a positive value of  indicates the existence of an electron-deficient reaction center in the rate-determining step (r.d.s.). The reaction experiences steric acceleration due to the ortho-substituents. An appropriate mechanism has been suggested.

Keywords

Benzaldehydes Correlation Halochromate Mechanism Oxidation

References

  • [1] E.J. Corey and W.J. Suggs, Pyridinium chlorochromate. An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds. Tetrahedron letters,, 16(31) (1975) 2647-2650.
  • [2] F.S. Guziec and F.A. Luzio, Synthesis, 9 (1975) 691-695.
  • [3] M.N. Bhattacharjee, M.K. Choudhuri, H.S. Dasgupta, N. Roy and D.R. Khathing, Synthesis, 7 (1982) 588-593.
  • [4] K. Balasubramanian and V. Prathiba, Indian J. Chem., 25B (1986) 326-331.
  • [5] A. Pandurangan, V. Murugesan and P. Palamichamy, J. Indian Chem. Soc., 72 (1995) 479-482.
  • [6] S. Mahajan, B. Sinhg, V.S. Jasrotia, M. Sharma, H.N. Sheikh and B.L. Kalsotra, Oxid. Commun.,31(2), 2008, 356-364
  • [7] D. Chandora, P. Bishnoi, G. Ram, O. Prakash and V. Sharma, Orient J. Chem.,37(6) (2021) 1329-1335.
  • [8] D. Yajurvedi, O. Prakash and A. Choudhary, 11(2) 2023, 57-68.
  • [9] D. Kumar, M. Baghmar and A. Choudhary, Res. J. Chem. Environ., 27(4) (2023) 101–106.
  • [10] R. Kalla, D. Kumar, A. Choudhary and V. Sharma, Oxidation kinetics and mechanistic studies of thioacids by imidazolium dichromate. Rasayan Journal of Chemistry14(4) (2021) 2436-2441.
  • [11] J. Kalpan, Deuterium Isotope Effects in the Bromine Oxidation of Ethanol and of Acetaldehyde1. Journal of the American Chemical Society, 80(11) (1958) 2639-2642.
  • [12] K.B. Wiberg, The deuterium isotope effect of some ionic reactions of benzaldehyde. Journal of the American Chemical Society 76 (1954) 5371-5375.
  • [13] H.C. Brown, G.C. Rao and S.U. Kulkarni, Stoichiometry of the oxidation of primary alcohols with pyridinium chlorochromate. Evidence for a two-electron change. The Journal of Organic Chemistry44 (1979) 2809-2810.
  • [14] M.N. Bhattacharjee, M.K. Choudhuri, S. Purakayastha, 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, 43(1987) 5389-5392.
  • [15] L. Liu and W.E. Guo, Isokinetic relationship, isoequilibrium relationship, and enthalpy− entropy compensation. Chemical reviews, 101(3) (2001) 673-696
  • [16] O. Exner, Prog. Phys. Org. Chem., 10 (1973) 411.
  • [17] M.J. Kamlet, J.L.M. Abboud, M.H. Abraham and R.W. Taft, Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters,. pi.*,. alpha., and. beta., and some methods for simplifying the generalized solvatochromic equation. The Journal of Organic Chemistry,48 (1983) 2877-2887.
  • [18] O. Exner, Additive physical properties. I. General relationships and problems of statistical nature. Collection of Czechoslovak Chemical Communications, 31 (1966) 3222-3251.
  • [19] C.G. Swain, M.S. Swain, A.L. Powel and S. Alunni, Antioxidant activity of phenols related to vitamin E. Are there chain-breaking antioxidants better than. alpha.-tocopherol?. Journal of the American Chemical Society, 105(3) (1983) 492-502.
  • [20] C.D. Johnson, The Hammett equation, University Press, Cambridge, (1973) 78.
  • [21] S.K. Dayal, S. Ehrenson and R.W. Taft, Substituent effects, electronic transmission, and structural dependence of. pi. delocalization as studied with the p-fluorophenyl tag. Journal of the American Chemical Society, 94(26) (1972) 9113-9122.
  • [22] C.G. Swain, S.H. Unger, N.R. Rosenquest and M.S. Swain, Substituent effects on chemical reactivity. Improved evaluation of field and resonance components. Journal of the American Chemical Society, 105(3) (1972) 492-502.
  • [23] M. Charton and B. Charton, Bull. Soc. Chim. Fr., (1988) 199-210 and references cited therein.
  • [24] M. Charton, Nature of the ortho effect. XI. Reaction rates of carboxylic acids with diazodiphenylmethane. The Journal of Organic Chemistry, 40(4) (1975) 407-411.
  • [25] E.S. Gould, Mechanism & structure in organic chemistry, Holt, Rinehart & Winston Inc., NY (1964).
There are 25 citations in total.

Details

Primary Language English
Subjects Reaction Kinetics and Dynamics
Journal Section Research Article
Authors

Ketul Kumawat

Anurag Choudhary 0000-0002-9313-2525

Om Prakash

Early Pub Date August 19, 2024
Publication Date January 5, 2025
Submission Date February 27, 2024
Acceptance Date July 23, 2024
Published in Issue Year 2025 Volume: 9 Issue: 1

Cite

APA Kumawat, K., Choudhary, A., & Prakash, O. (2025). CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE. Turkish Computational and Theoretical Chemistry, 9(1), 53-62. https://doi.org/10.33435/tcandtc.1443581
AMA Kumawat K, Choudhary A, Prakash O. CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE. Turkish Comp Theo Chem (TC&TC). January 2025;9(1):53-62. doi:10.33435/tcandtc.1443581
Chicago Kumawat, Ketul, Anurag Choudhary, and Om Prakash. “CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE”. Turkish Computational and Theoretical Chemistry 9, no. 1 (January 2025): 53-62. https://doi.org/10.33435/tcandtc.1443581.
EndNote Kumawat K, Choudhary A, Prakash O (January 1, 2025) CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE. Turkish Computational and Theoretical Chemistry 9 1 53–62.
IEEE K. Kumawat, A. Choudhary, and O. Prakash, “CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE”, Turkish Comp Theo Chem (TC&TC), vol. 9, no. 1, pp. 53–62, 2025, doi: 10.33435/tcandtc.1443581.
ISNAD Kumawat, Ketul et al. “CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE”. Turkish Computational and Theoretical Chemistry 9/1 (January 2025), 53-62. https://doi.org/10.33435/tcandtc.1443581.
JAMA Kumawat K, Choudhary A, Prakash O. CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE. Turkish Comp Theo Chem (TC&TC). 2025;9:53–62.
MLA Kumawat, Ketul et al. “CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE”. Turkish Computational and Theoretical Chemistry, vol. 9, no. 1, 2025, pp. 53-62, doi:10.33435/tcandtc.1443581.
Vancouver Kumawat K, Choudhary A, Prakash O. CORRELATION ANALYSIS OF STRUCTURE & REACTIVITY IN THE OXIDATION OF AROMATIC ALDEHYDES BY 2-PICOLINIUM CHLOROCHROMATE. Turkish Comp Theo Chem (TC&TC). 2025;9(1):53-62.
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Journal Full Title: Turkish Computational and Theoretical Chemistry


Journal Abbreviated Title: Turkish Comp Theo Chem (TC&TC)