Advertisement

Modified Silico-Tungstate: An Easy and Efficient Catalyst for the Acetylation of Amines Under Solvent-Free Condition

  • R. K. Sharma
  • Deepti Rawat
Article

Abstract

In this present work, organo-functionalization of silica gel was carried out using 3-aminopropyltriethoxysilane (APTES) as a reactive surface modifier. Tungstate ion (WO4 2−) was immobilized onto the modified silica gel and its catalytic activity was investigated for acetylation of amines under solvent-free conditions. The method is highly chemoselective—amine group was selectively acetylated in presence of the hydroxyl group. The above catalyst gave acetylated products in excellent yield in shorter duration of time. The catalyst was characterized by various techniques such as BET surface area measurements, FTIR, CHNS, 13C-CPMAS-NMR, ED-XRF and diffuse reflectance UV–vis techniques. The catalyst was reused five times without significant loss of catalytic activity.

Graphical Abstract

In this present work, organo-functionalization of silica gel was carried out using 3-aminopropyltriethoxysilane (APTES) as a reactive surface modifier. Tungstate ion (WO4 2−) was immobilized onto the modified silica gel and its catalytic activity was investigated for acetylation of amines under solvent-free conditions. The method is highly chemoselective—amine group was selectively acetylated in presence of the hydroxyl group. The above catalyst gave acetylated products in excellent yield in shorter duration of time. The catalyst was characterized by various techniques such as BET surface area measurements, FTIR, CHNS, 13C-CPMAS-NMR, ED-XRF and diffuse reflectance UV–vis techniques. The catalyst was reused five times without significant loss of catalytic activity.

Keywords

Acetylation Amines Modified silica Tungstate Solvent-free 

References

  1. 1.
    T.W. Green, P.G.M. Wuts, Protective Groups in Organic Chemistry (Wiley, New York, 1991)Google Scholar
  2. 2.
    A.L. Pearson, W.J. Roush, Handbook of Reagents for Organic Synthesis: Activating Agents and Protecting Groups (Wiley, London, 1999)Google Scholar
  3. 3.
    P.J. Kocienski, Protecting Groups (Georg Thieme Verlag, New York, 1994)Google Scholar
  4. 4.
    W. Steglich, G. Hofle, Angew. Chem. Int. Ed. Engl. 8, 981 (1969)CrossRefGoogle Scholar
  5. 5.
    R.I. Zhdanov, S.M. Zhenodarova, Synthesis 222 (1975)Google Scholar
  6. 6.
    G. Hofle, W. Steglich, H. Vorbruggen, Angew. Chem. Int. Ed. Engl. 17, 569 (1978)CrossRefGoogle Scholar
  7. 7.
    E. Vedejs, N.S. Bennett, L.M. Conn, S.T. Diver, M. Gingras, S. Lin, P.A. Oliver, M.J. Peterson, J. Org. Chem. 58, 7286 (1993)CrossRefGoogle Scholar
  8. 8.
    R.H. Backer, F.G. Bordwell, Org. Synth. 3, 141 (1955)Google Scholar
  9. 9.
    J. Iqbal, R.R. Srivastava, J. Org. Chem. 57, 2001 (1992)CrossRefGoogle Scholar
  10. 10.
    J.S. Yadav, A.V. Narsaiah, A.K. Basak, P.R. Goud, D. Sreenu, K. Nagaiah, J. Mol. Catal. A: Chem. 255, 78 (2006)CrossRefGoogle Scholar
  11. 11.
    K. Jeyakumar, D.K. Chand, J. Mol. Catal. A: Chem. 255, 275 (2006)CrossRefGoogle Scholar
  12. 12.
    S. Kanta De, Tetrahedron Lett. 45, 2919 (2004)CrossRefGoogle Scholar
  13. 13.
    P. Phukan, Tetrahedron Lett. 45, 4785 (2004)CrossRefGoogle Scholar
  14. 14.
    M.L. Kantam, K. Aziz, P.R. Likhar, Catal. Commun. 7, 484 (2006)CrossRefGoogle Scholar
  15. 15.
    S. Chandrasekhar, T. Ramchander, M. Takhi, Tetrahedron Lett. 39, 3263 (1998)CrossRefGoogle Scholar
  16. 16.
    A.K. Chakraborti, R. Gulhane, Tetrahedron Lett. 44, 6749 (2003)CrossRefGoogle Scholar
  17. 17.
    R. Ghosh, S. Maiti, A. Chakraborti, Tetrahedron Lett. 46, 147 (2005)CrossRefGoogle Scholar
  18. 18.
    A. Orita, C. Tanahashi, A. Kakuda, J. Otera, Angew. Chem. Int. Ed. 39, 2877 (2000)Google Scholar
  19. 19.
    P. Saravanan, V.K. Singh, Tetrahedron Lett. 40, 2611 (1999)CrossRefGoogle Scholar
  20. 20.
    K.L. Chandra, P. Saravanan, R.K. Singh, V.K. Singh, Tetrahedron 58, 1369 (2002)CrossRefGoogle Scholar
  21. 21.
    R. Alleti, M. Perambuduru, S. Samantha, V.P. Reddy, J. Mol. Catal. A: Chem. 226, 57 (2005)CrossRefGoogle Scholar
  22. 22.
    A. Kamal, M.N.A. Khan, K.S. Reddy, Y.V.V. Srikanth, T. Krishnaji, Tetrahedron Lett. 48, 3813 (2007)CrossRefGoogle Scholar
  23. 23.
    R. Dalpozzo, A. De Nino, L. Maiuolo, A. Procopio, M. Nardi, G. Bartoli, M. Romeo, Tetrahedron Lett. 44, 5621 (2003)CrossRefGoogle Scholar
  24. 24.
    A.G. Barrett, D.C. Braddock, Chem. Commun. 351 (1997)Google Scholar
  25. 25.
    S.G. Lee, J.H. Park, J. Mol. Catal. A: Chem. 194, 49 (2003)CrossRefGoogle Scholar
  26. 26.
    H. Firouzabadi, N. Iranpoor, F. Nowrouzi, K. Amani, Chem. Commun. 764 (2003)Google Scholar
  27. 27.
    J.K. Joseph, S.L. Jain, B. Sain, J. Mol. Catal. A: Chem. 267, 108 (2007)CrossRefGoogle Scholar
  28. 28.
    K. Shimizu, T. Higuchi, E. Takasugi, T. Hatamachi, T. Kodama, A. Satuma, J. Mol. Catal. A: Chem. 284, 89 (2008)CrossRefGoogle Scholar
  29. 29.
    T.S. Jin, Y.R. Ma, Z.H. Zhang, T.S. Li, Synth. Commun. 28, 3173 (1998)CrossRefGoogle Scholar
  30. 30.
    B. Das, P. Thirupathi, J. Mol. Catal. A: Chem. 269, 12 (2007)CrossRefGoogle Scholar
  31. 31.
    S.T. Kadam, S.S. Kim, Synthesis 267 (2008)Google Scholar
  32. 32.
    H.J. Yoon, S.M. Lee, J.H. Kim, H.J. Cho, J.W. Choi, S.H. Lee, Y.S. Lee, Tetrahedron Lett. 49, 3165 (2008)CrossRefGoogle Scholar
  33. 33.
    K. Ishihara, A. Hasegawa, H. Yamamoto, Angew. Chem. Int. Ed. 40, 4077 (2001)CrossRefGoogle Scholar
  34. 34.
    S. Farhadi, M. Zaidi, J. Mol. Catal. A: Chem. 299, 18 (2009)CrossRefGoogle Scholar
  35. 35.
    F. Rajabi, Tetrahedron Lett. 50, 395 (2009)CrossRefGoogle Scholar
  36. 36.
    R.K. Sharma, Pure Appl. Chem. 73, 181 (2001)CrossRefGoogle Scholar
  37. 37.
    R.K. Sharma, S. Mittal, M. Koel, Crit. Rev. Anal. Chem. 33, 183 (2003)CrossRefGoogle Scholar
  38. 38.
    R.K. Sharma, A. Goel, Anal. Chimica. Act. 534, 137 (2005)CrossRefGoogle Scholar
  39. 39.
    R. Gupta, V. Kumar, M. Gupta, S. Paul, Ind. J. Chem. 47, 1739 (2008)Google Scholar
  40. 40.
    T.S. Reddy, M. Narasimhulu, N. Suryakiran, K.C. Mahesh, K. Ashalatha, Y. Venkateswarlu, Tetrahedron Lett. 47, 6825 (2006)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  1. 1.Green Chemistry Network Centre, Department of ChemistryUniversity of DelhiDelhiIndia

Personalised recommendations