Skip to main content
SpringerLink
Log in

β-Cyclodextrin promoted oxidation of primary amines to nitriles in water

  • Research Article
  • Published:
Frontiers of Chemical Engineering in China Aims and scope Submit manuscript

Abstract

A facile, efficient and substrate-selective oxidation of the primary amines with NaClO as oxidant catalyzed by β-cyclodextrin (β-CD) has been developed in water for the first time, and the behavior of β-cyclodextrin that catalyzed the primary amines to nitriles in water was investigated. It was found that the primary amines which could form host-guest complexes with β-cyclodextrin were oxidized to nitriles with excellent yields at ambient temperature. The results show that β-cyclodextrin worked not only as a solubilizing agent but also as a catalyst in these reactions.

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

Similar content being viewed by others

References

  1. Ji H B, She Y B. Green oxidation and reduction. Beijing: China Petrochemical press, 2005 (in Chinese)

    Google Scholar 

  2. Huang X, Wang Y G, Chen Z C. New organic synthesis chemistry. Beijing: Chemical industry press, 2003 (in Chinese)

    Google Scholar 

  3. Brzaszcz M, Kloc K, Mlochowski J. Hydroperoxide oxidation of benzylamines catalyzed by selenium compounds. Pol J Chem, 2003, 77: 1579–1586

    CAS  Google Scholar 

  4. El Hendawy A M, Alqaradawi S Y, Al Madfa H A. Ruthenium(III) mono (2,2′-bipyridine) complexes containing O,O-donor ligands and their oxidation properties for organic compounds. Transition Met Chem, 2000, 25: 572–578

    Article  Google Scholar 

  5. Mori K, Yamaguchi K, Mizugaki T, Ebitani K, Kaneda K. Catalysis of a hydroxyapatite-bound Ru complex: efficient heterogeneous oxidation of primary amines to nitriles in the presence of molecular oxygen. Chem Commun, 2001, 461–462

  6. Yamaguchi K, Mizuno N. Scope, kinetics, and mechanistic aspects of aerobic oxidations catalyzed by ruthenium supported on alumina. Chem Eur J, 2003, 9: 4353–4361

    Article  CAS  Google Scholar 

  7. Chen F E, Peng Z Z, Fu H, Liu J D, Shao L Y. Tetrabutylammonium peroxydisulfate in organic synthesis. Part 8. An efficient and convenient nickel-catalyzed oxidation of primary amines to nitriles with tetrabutylammonium peroxydisulfate. J Chem Research (Suppl), 1999, 726–727

  8. Yamazaki S. A simple and convenient method for the synthesis of nitriles by oxidation of primary amines with NaClO in ethanol. Synth Commun, 1997, 27: 3559–3564

    Article  CAS  Google Scholar 

  9. Surendra K, Krishnaveni N S, Reddy M A, Nageswar Y V D, Rao K R. Mild oxidation of alcohols with o-iodoxybenzoic acid (IBX) in water/acetone mixture in the presence of beta-cyclodextrin. J Org Chem, 2003, 68: 2058–2059

    Article  CAS  Google Scholar 

  10. Marinescu L, Molbach M, Rousseau C, Bols M. Supramolecular oxidation of anilines using hydrogen peroxide as stoichiometric oxidant. J Am Chem Soc, 2005, 127: 17578–17579

    Article  CAS  Google Scholar 

  11. Ji H B, Shi D P, Shao M, Li Z, Wang L F. Transition metal-free and substrate-selective oxidation of alcohols using water as an only solvent in the presence of beta-cyclodextrin. Tetrahedron Lett, 2005, 46: 2517–2520

    Article  CAS  Google Scholar 

  12. Ji H B. Highly shape-selective, biomimetic, and efficient deprotection of carbonyl compounds masked as ethylene acetals or dioxolanes produced from 1,2-ethanediol. Eur J Org Chem, 2003, 3659–3662

  13. Ji H B, Hu X F, Shi D P, Li Z. Controllable oxidation of sulfides to sulfoxides and sulfones with aqueous hydrogen peroxiades in the presence of beta-cyclodextrin. Russ J Org Chem, 2006, 42: 959–961

    Article  CAS  Google Scholar 

  14. Surendra K, Krishnaveni N S, Rao K R. A simple biomimetic protocol for the oxidation of alcohols with sodium hypochlorite in the presence of beta-cyclodextrin in water. Can J Chem, 2004, 82: 1230–1233

    Article  CAS  Google Scholar 

  15. Reddy M A, Surendra K, Bhanumathi N, Rao K R. Highly facile biomimetic regioselective ring opening of epoxides to halohydrins in the presence of beta-cyclodextrin. Tetrahedron, 2002, 58: 6003–6008

    Article  CAS  Google Scholar 

  16. Fan Z, Diao C H, Song H B, Jing Z L, Yu M, Chen X, Guo M J. Encapsulation of Quinine by β-Cyclodextrin: excellent model for mimicking enzyme-substrate interactions. J Org Chem, 2006, 71: 1244–1246

    Article  CAS  Google Scholar 

  17. Báscuas J, García-Río L, Leis J R, Méndez-Pérez M. Cyclodextrin effect on solvolysis of ortho benzoyl chlorides. J Incl Phenom Macrocycl Chem, 2007, 57: 603–606

    Article  Google Scholar 

  18. Surendra K, Krishnaveni N S, Reddy M A, Nageswar Y V D, Rao K R. Highly selective oxidative cleavage of β-cyclodextrin-epoxide/aziridine complexes with IBX in water. J Org Chem, 2003, 68: 9119–9121

    Article  CAS  Google Scholar 

  19. Surendra K, Krishnaveni N S, Nageswar Y V D, Rao K R. Highly regioselective ring opening of oxiranes with phenoxides in the presence of β-cyclodextrin in water. J Org Chem, 2003, 68: 4994–4995

    Article  CAS  Google Scholar 

  20. Tong L H. Cyclodextrin chemistry-base and application. Beijing: Science Press, 2001 (in Chinese)

    Google Scholar 

  21. Breslow R. Biomimetic control of chemical selectivity. Acc Chem Res, 1980, 13: 170–177

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China

    Dongpo Shi, Hongbing Ji & Zhong Li

Authors
  1. Dongpo Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hongbing Ji
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hongbing Ji.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shi, D., Ji, H. & Li, Z. β-Cyclodextrin promoted oxidation of primary amines to nitriles in water. Front. Chem. Eng. China 3, 196–200 (2009). https://doi.org/10.1007/s11705-009-0051-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-009-0051-6

Keywords

Search

Navigation