Skip to main content
SpringerLink
Log in

Kinetics and mechanism of oxidation of N,α-diphenylnitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) in aqueous DMF medium

  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Abstract

The kinetics of oxidation of aldonitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) has been studied in aqueous N,N-dimethylformamide in the presence of perchloric acid. The reaction follows first-order kinetics with respect to each of DMAPCC and nitrone. The order with respect to [H+] was found to be close to zero. The rate of oxidation was unaltered by the variation of [NaClO4] but addition of MnSO4 decreased the rate. The reaction rate was found to decrease with a decrease in dielectric constant of the medium. Electron-releasing and electron-withdrawing groups perturb the reaction rate with a good Hammett correlation. The oxidation products were found to be benzaldehyde and nitrosobenzene. The reaction was carried out at four different temperatures and the activation parameters have been calculated. On the basis of the experimental findings, a suitable mechanism has been proposed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Guziec FS, Luzzio FA (1982) J Org Chem 47:1981

    Article  Google Scholar 

  2. Mohammadpoor Baltork I, Kharmesh B (1998) J Chem Res Synop 3:146

    Google Scholar 

  3. Uma M, Gopalakrishnan M, Jayabharathi J, Thanikachalam V (1995) Indian J Chem 34B:612

    CAS  Google Scholar 

  4. Uma M, Gopalakrishnan M, Jayabharathi J, Thanikachalam V (1996) J Indian Chem Soc 73:92

    Google Scholar 

  5. Gopalakrishnan M, Jayabharathi J, Thanikachalam V (1999) Asian J Chem 11:1459

    CAS  Google Scholar 

  6. Gopalakrishnan M, Uma M, Jayabharathi J, Thanikachalam V (2002) Afinidad 591:688

    Google Scholar 

  7. Gopalakrishnan M, Jayabharathi J, Uma M, Thanikachalam V (2007) Oxid Commun 30:625

    CAS  Google Scholar 

  8. Studinger H, Niescher K (1919) Helv Chim Acta 2:554

    Article  Google Scholar 

  9. Ageli S, Bigiavi D 5:822; Beilsteins Handbuch Der Organischen Chemie 12II:116 (1950)

  10. Bellavita V (1935) Gazz Chim Ital 65:889; (1936) Chem Abstr 30:3419

  11. Angeli S, Valori RAL 5, 2II:731; Beilsteins Handbuch Der Organischen Chemie 21I:172 (1933)

  12. Beckmann E (1909) Ann Chim Applic 367:271

    Google Scholar 

  13. Bamberger E (1924) Ber Dtsch Chem Ges 57:2082

  14. Grammticakis P (1951) Bull Chem Soc Fr 956; (1952) Chem Abstr 46:11133

  15. Bradley GM, Strauss HL (1975) J Phys Chem 79:1953

    Article  CAS  Google Scholar 

  16. Mangalam G, Gurumurthy R, Arul R, Karthikeyan R (1996) Indian J Chem 35B:413

    CAS  Google Scholar 

  17. Nagarajan K, Sundaram S, Venkatasubramanian N (1979) Indian J Chem 18A:335

    CAS  Google Scholar 

  18. Perez-Benito JF, Arias C, Lamrhari D (1992) J Chem Soc Chem Commun 472

  19. Huber CF, Haight GP Jr (1976) J Am Chem Soc 98:4128

    Article  CAS  Google Scholar 

  20. Olatunji MA, Ayoko GA (1988) Polyhedron 7:11

    Article  CAS  Google Scholar 

  21. Gaswick DC, Krueger JH (1969) J Am Chem Soc 91:2240

    Article  CAS  Google Scholar 

  22. Khan Z, Yousuf Dar M, Babe PSS (2004) Indian J Chem 42A:1060

    Google Scholar 

  23. March J (1968) Advanced organic chemistry: reactions, mechanisms and structure. McGraw Hill Book Company, New York, p 241

    Google Scholar 

  24. Gilberson NR, Gallup GA, Jones MM (1954) Trans Kans Acad Sci 57:391; Leffler JE (1955) J Chem Phys 23:2199

    Google Scholar 

  25. Exner O (1964) Collect Czech Chem Commun 29:1094

    CAS  Google Scholar 

  26. Singh AK, Chopra D, Rahmani S, Singh B (1998) Carbohydr Res 314:157

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Annamalai University, Annamalainagar, 608 002, Tamil Nadu, India

    Govindasamy Rajarajan, Subramaniyan Manivarman, Jayaraman Jayabharathi & Venugopal Thanikachalam

  2. Department of Chemistry, Pachaiyappa’s College, Chennai, 600 030, India

    Natesan Jayachandramani

Authors
  1. Govindasamy Rajarajan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Natesan Jayachandramani
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Subramaniyan Manivarman
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jayaraman Jayabharathi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Venugopal Thanikachalam
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Venugopal Thanikachalam.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rajarajan, G., Jayachandramani, N., Manivarman, S. et al. Kinetics and mechanism of oxidation of N,α-diphenylnitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) in aqueous DMF medium. Transition Met Chem 33, 393–397 (2008). https://doi.org/10.1007/s11243-008-9055-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11243-008-9055-1

Keywords

Search

Navigation