Skip to main content
SpringerLink
Log in

1,4-Dihydroxyanthraquinone-copper(II) nanoparticles immobilized on silica gel: a highly efficient, copper scavenger and recyclable heterogeneous nanocatalyst for a click approach to the three-component synthesis of 1,2,3-triazole derivatives in water

  • Original Paper
  • Published:
Journal of the Iranian Chemical Society Aims and scope Submit manuscript

Abstract

High yielding preparation of structurally different β-hydroxy 1,4-disubstituted 1,2,3-triazole from the regio-selective reaction of epoxides 2a–2c with wide range of terminal alkynes 1a–1j, and sodium azide in the presence of catalytic amount, complexed form of homogeneous catalyst [bis 1,4-mono ester hydroxy anthraquinone copper(II)] (5.0 mol%), [AQ2Cu(II)] 7 at 25 °C in water has been described. To benefit from the recovery and reuse of the catalyst, a novel heterogeneous nanoparticles of catalyst [bis 1,4-mono ester hydroxy anthraquinone copper(II) aminopropyl silica gel] (5.0 mol%), [AQ2Cu(II)-APSiO2] 13 bearing oxygen anthraquinone ligands with strong copper(II) affinity was easily prepared by using silica gel as a suitable support. The heterogeneous catalyst was fully characterized by XRD, SEM, AFM, ICP, TG methods for analysis of nitrogen adsorption, and FT-IR techniques. The remarkable features of this protocol are high yields, short reaction times, a cleaner reaction profile in an environmentally benign solvent (H2O), one-pot procedure and the method is applicable to large-scale operation without any problem. Furthermore, the catalyst could be recovered and easily removed by simple filtration of the reaction mixture and it was recycled ten times showing negligible copper leaching. In their uncomplexed form of homogeneous catalyst [AQ2Cu(II)] 7 and heterogeneous catalyst [AQ2Cu(II)-APSiO2] 13, the anthraquinone ligand 6 and [AQ-APSiO2] 12 are very efficient copper scavengers able to catalyze the 1,3-dipolar cycloaddition reaction of azides with alkynes (CuAAC) without pre-synthesis of catalysts.

Graphical Abstract

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

Scheme 1
Scheme 2
Scheme 3
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. B.S. Holla, M. Mahalinga, M.S. Karthikeyan, B. Poojary, P.M. Akberali, N.S. Kumari, Eur. J. Med. Chem. 40, 1173 (2005)

    Article  CAS  Google Scholar 

  2. K. Dabak, O. Sezer, A. Akar, O. Anac, Eur. J. Med. Chem. 38, 215 (2003)

    Article  CAS  Google Scholar 

  3. W.S. Horne, M.K. Yadav, C.D. Stout, M.R. Ghadiri, J. Am. Chem. Soc. 126, 15366 (2004)

    Article  CAS  Google Scholar 

  4. A.D. Moorhouse, A.M. Santos, M. Gunaratnam, M. Moore, S. Neidle, J.E. Moses, J. Am. Chem. Soc. 128, 15972 (2006)

    Article  CAS  Google Scholar 

  5. A.D. Moorhouse, J.E. Moses, Chem. Med. Chem. 3, 715 (2008)

    CAS  Google Scholar 

  6. C. Mamat, T. Ramenda, F.R. Wuest, Mini-Rev. Org. Chem. 6, 21 (2009)

    Article  CAS  Google Scholar 

  7. M.D. Best, Biochemistry 48, 6571 (2009)

    Article  CAS  Google Scholar 

  8. M. Whiting, J.C. Tripp, Y.C. Lin, W. Lindstrom, A.J. Olson, J.H. Elder, K.B. Sharpless, V.V. Fokin, J. Med. Chem. 49, 7697 (2006)

    Article  CAS  Google Scholar 

  9. M.J. Giffin, H. Heaslet, A. Brik, Y.-C. Lin, G. Cauvi, C.-H. Wong, D.E. McRee, J.H. Elder, C.D. Stout, B.E. Torbett, J. Med. Chem. 51, 6263 (2008)

    Article  CAS  Google Scholar 

  10. S.H. Kim, H.S. Choi, J. Kim, S.J. Lee, D.T. Quang, J.S. Kim, Org. Lett. 12, 560 (2010)

    Article  CAS  Google Scholar 

  11. L.-F. Lutz, Angew. Chem. Int. Ed. 46, 1018 (2007)

    Article  CAS  Google Scholar 

  12. J. Zhan, D. Tian, H. Li, New J. Chem. 33, 725 (2009)

    Article  CAS  Google Scholar 

  13. S.Y. Park, J.H. Yoon, C.S. Hong, R. Souane, J.S. Kim, S.E. Matthews, J. Vicens, J. Org. Chem. 73, 8212 (2008)

    Article  CAS  Google Scholar 

  14. K. Chang, L. Su, A. Senthilvelan, W. Chung, Org. Lett. 9, 3363 (2007)

    Article  CAS  Google Scholar 

  15. V. Haridas, K. Lal, Y.K. Sharma, S. Upreti, Org. Lett. 10, 1645 (2008)

    Article  CAS  Google Scholar 

  16. P. Wu, M. Malkoch, J.N. Hunt, R. Vestberg, E. Kaltgrad, M.G. Finn, V.V. Fokin, K.B. Sharpless, C.J. Hawker, Chem. Commun. 48, 5775 (2005)

    Article  Google Scholar 

  17. G. Franc, A.K. Kakkar, Chem. Eur. J. 15, 5630 (2009)

    Article  CAS  Google Scholar 

  18. R. Huisgen, Angew. Chem. Int. Ed. Engl. 2, 565 (1963)

    Article  Google Scholar 

  19. K.V. Gothelf, K.A. Jorgensen, Chem. Rev. 98, 863 (1998) (see the references cited therein)

  20. R. Huisgen, 1,3-Dipolar cycloaddition chemistry, chap 1 A. Padwa (ed.) (Wiley, New York, 1984) p. 1

  21. M. Liu, O. Reiser, 1,3-Dipolar cycloaddition chemistry, Org. Lett. 13, 1102 (2011) (see the references cited therein)

  22. C. Spiteri, J.E. Moses, Angew. Chem. Int. Ed. 49, 31 (2010)

    Article  CAS  Google Scholar 

  23. M. Fuchs, W. Goessler, C. Pilger, C.O. Kappe, Adv. Synth. Catal. 352, 323 (2010)

    Article  CAS  Google Scholar 

  24. G.-C. Kuang, H.A. Michaels, J.T. Simmons, R.J. Clark, L. Zhu, J. Org. Chem. 75, 6540 (2010)

    Article  CAS  Google Scholar 

  25. A.E. Cohrt, J.F. Jensen, T.E. Nielsen, Org. Lett. 12, 5414 (2010)

    Article  CAS  Google Scholar 

  26. J. T. Fletcher, M. E. Keeney, S. E. Walz, Synthesis 19, 3339 (2010)

    Google Scholar 

  27. M. Xu, C. Kuang, Z. Wang, Q. Yang, Y. Jiang. Synthesis 2, 223 (2011)

    Google Scholar 

  28. S. Chandrasekhar, M. Seenaiah, A. Kumar, C.R. Reddy, S.K. Mamidyal, C.G. Kumar, S. Balasubramanian, Tetrahedron Lett. 52, 806 (2011)

    Article  CAS  Google Scholar 

  29. K.D. Hänni, D.A. Leigh, Chem. Soc. Rev. 39, 1240 (2010)

    Article  Google Scholar 

  30. J.M. Holub, K. Kirshenbaum, Chem. Soc. Rev. 39, 1325 (2010)

    Article  CAS  Google Scholar 

  31. F. Santoyo-Gonzalez, F. Hernandez-Mateo, Chem. Soc. Rev. 38, 3449 (2009)

    Article  CAS  Google Scholar 

  32. R.A. Decre’au, J.P. Collman, A. Hosseini, Chem. Soc. Rev. 39, 1291 (2010)

    Article  Google Scholar 

  33. P. Appukkuttan, V.P. Mehtaa, E. Van der Eycken, Chem. Soc. Rev. 39, 1467 (2010)

    Article  CAS  Google Scholar 

  34. D. Wang, Na. Li, M. Zhao, W. Shi, C. Ma, B. Chen, Green Chem. 12, 2120 (2010) (see references therein)

  35. C.Le. Droumaguet, C. Wang, Q. Wang, Chem. Soc. Rev. 39, 1233 (2010)

    Article  Google Scholar 

  36. C.O. Kappe, E. Van der Eycken, Chem. Soc. Rev. 39, 1280 (2010)

    Article  CAS  Google Scholar 

  37. A.H. El-Sagheer, T. Brown, Chem. Soc. Rev. 39, 1388 (2010)

    Article  CAS  Google Scholar 

  38. H.C. Kolb, M.G. Finn, K.B. Sharpless, Angew. Chem. Int. Ed. 40, 2004 (2001)

    Article  CAS  Google Scholar 

  39. M.G. Finn, V.V. Fokin, Chem. Soc. Rev. 39, 1231 (2010)

    Article  CAS  Google Scholar 

  40. S.K. Mamidyala, M.G. Finn, Chem. Soc. Rev. 39, 1252 (2010)

    Article  CAS  Google Scholar 

  41. C.E. Hoyle, A.B. Lowe, C.N. Bowman, Chem. Soc. Rev. 39, 1355 (2010)

    Article  CAS  Google Scholar 

  42. D. Urankar, M. Steinbucher, J. Kosjek, J. Kosmrlj, Tetrahedron 66, 2602 (2010)

    Article  CAS  Google Scholar 

  43. H. Elamari, F. Meganem, J. Herscovici, C. Girard, Tetrahedron Lett. 52, 658 (2011)

    Article  CAS  Google Scholar 

  44. T. Nakamura, T. Terashima, K. Ogata, S.I. Fukuzawa, Org. Lett. 13, 620 (2011)

    Article  CAS  Google Scholar 

  45. V.V. Rostovtsev, L.G. Green, V.V. Fokin, K.B. Sharpless, Angew. Chem. Int. Ed. 41, 2596 (2002)

    Article  CAS  Google Scholar 

  46. K.B. Sharpless, V.V. Fokin, L.G. Green, V.V. Rostovtsev, Angew. Chem. Int. Ed. 114, 2708 (2002)

    Article  Google Scholar 

  47. C.W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 67, 3057 (2002)

    Article  Google Scholar 

  48. M. Meldal, C.W. Tornøe, Chem. Rev. 108, 2952 (2008) (see the references cited therein)

  49. J.E. Hein, V.V. Fokin, Chem. Soc. Rev. 39, 1302 (2010) (see the references cited therein)

    Google Scholar 

  50. W.S. Brotherton, H.A. Michaels, J.T. Simmons, R.J. Clark, N.S. Dalal, L. Zhu, Org. Lett. 11, 4954 (2009)

    Article  CAS  Google Scholar 

  51. H. Sharghi, M. H. Beyzavi, A. Safavi, M. M. Doroodmand, R. Khalifeh, Adv. Synth. Catal. 351, 2391 (2009) (see the references cited therein)

    Google Scholar 

  52. L. Durán Pachón, J.H. Van Maarseveen, G. Rothenberg, Adv. Synth. Catal. 347, 811 (2005)

    Article  Google Scholar 

  53. T. Miao, L. Wang, Synthesis 3, 363 (2008)

  54. A. Coelho, P. Diz, O. Caamano, E. Sotelo, Adv. Synth. Catal. 352, 179 (2010)

    Google Scholar 

  55. S. Chassing, M. Kumarraja, A.S.S. Sido, P. Pale, J. Sommer, Org. Lett. 9, 883 (2007)

    Article  Google Scholar 

  56. S. Chassaing, A.S.S. Sido, A. Alix, M. Kumarraja, P. Pale, J. Sommer, Chem. Eur. J. 14, 6713 (2008)

    Article  CAS  Google Scholar 

  57. P. Kuhn, A. Alix, M. Kumarraja, B. Louis, P. Pale, J. Sommer. Eur. J. Org. Chem. 3, 423 (2009)

    Google Scholar 

  58. V. Bénéteau, A. Olmos, T. Boningari, J. Sommer, P. Pale, Tetrahedron Lett. 51, 3673 (2010)

    Article  Google Scholar 

  59. K. Yamaguchi, T. Oishi, T. Katayama, N. Mizuno, Chem. Eur. J. 15, 10464 (2009)

    Article  CAS  Google Scholar 

  60. M.L. Kantam, V.S. Jaya, B. Sreedhar, M.M. Rao, B.M. Choudary, J. Mol. Catal. A. 256, 273 (2006)

    Article  CAS  Google Scholar 

  61. T. Katayama, K. Kamata, K. Yamaguchi, N. Mizuno, ChemSusChem 2, 59 (2009)

    Article  CAS  Google Scholar 

  62. C. Girard, E. Onen, M. Aufort, S. Beauviere, E. Samson, J. Herscovici, Org. Lett. 8, 1689 (2006)

    Article  CAS  Google Scholar 

  63. B. Lipshutz, B.R. Taft, Angew. Chem. Int. Ed. 45, 8235 (2006)

    Article  CAS  Google Scholar 

  64. C.-T. Lee, S. Huang, B.H. Lipshutz, Adv. Synth. Catal. 351, 3139 (2009)

    Article  CAS  Google Scholar 

  65. F. Alonso, Y. Moglie, G. Radivoy, M. Yus, Adv. Synth. Catal. 352, 3208 (2010)

    Article  CAS  Google Scholar 

  66. F. Alonso, Y. Moglie, G. Radivoy, M. Yus, Tetrahedron Lett. 50, 2358 (2009)

    Article  CAS  Google Scholar 

  67. M. Chtchigrovsky, A. Primo, P. Gonzalez, K. Molvinger, M. Robitzer, F. Quignard, F. Taran, Angew. Chem. Int. Ed. 121, 6030 (2009)

    Article  Google Scholar 

  68. A. Megia-Fernandez, M. Ortega-Muñoz, J. Lopez-Jaramillo, F. Hernandez-Mateo, F. Santoyo-Gonzalez, Adv. Synth. Catal. 352, 3306 (2010)

    Article  CAS  Google Scholar 

  69. B.R. Buckley, S.E. Dann, H. Heaney, E.C. Stubbs, Eur. J. Org. Chem. 4, 770 (2011)

    Article  Google Scholar 

  70. L.A. Bigelow, H.H. Reynolds, Org. Synth. 6, 476 (1941)

    Google Scholar 

  71. J.W. Lown, Anthracycline and anthracenedione-based anticancer agents, chap IV. (Elsevier, 1988), pp. 129–161 (see references therein)

  72. T. Moriuchi, T. Watanabe, I. Ikeda, A. Ogawa, T. Hirao, Eur. J. Inorg. Chem. 1, 277 (2001)

    Article  Google Scholar 

  73. A. Quach, V. Escax, L. Nicole, P. Goldner, O. Guillot-Noël, P. Aschehoug, P. Hesemann, J. Moreau, D. Gourier, C. Sanchez, J. Mater. Chem. 17, 2552 (2007)

    Article  CAS  Google Scholar 

  74. M. Shamsipur, A. Besharati-Seidani, J. Fasihi, H. Sharghi, Talanta 83, 674 (2010)

    Article  CAS  Google Scholar 

  75. M. Barzegar, M.F. Mousavi, H. Khajesharifi, M. Shamsipur, H. Sharghi, IEEE Sens. J. 5, 392 (2005)

    Article  CAS  Google Scholar 

  76. A. Rahmani, M.F. Mousavi, S.M. Golabi, M. Shamsipur, H. Sharghi, Chem. Anal. 49, 359 (2004)

    CAS  Google Scholar 

  77. S. Riahi, M.F. Mousavi, M. Shamsipour, H. Sharghi, Electroanalysis 15, 1561 (2003)

    Article  CAS  Google Scholar 

  78. M. Shamsipur, A. Avanes, M. Javanbakht, M.R. Ganjali, H. Sharghi, Anal. Sci. 18, 875 (2002)

    Article  CAS  Google Scholar 

  79. M. Shamsipur, F. Raoufi, H. Sharghi, Talanta 52, 637 (2000)

    Article  CAS  Google Scholar 

  80. H. Sharghi, M.H. Beyzavi, M.M. Doroodmand, Eur. J. Org. Chem. 24, 4126 (2008)

    Article  Google Scholar 

  81. H. Sharghi, M. Aberi, M.M. Doroodmand, Adv. Synth. Catal. 350, 2380 (2008)

    Article  CAS  Google Scholar 

  82. H. Sharghi, A.R. Salimi-Beni, Synthesis 1, 2900 (2004)

    Article  Google Scholar 

  83. H. Sharghi, O. Asemani, R. Khalifeh, Synth. Commun. 38, 1128 (2008)

    Article  CAS  Google Scholar 

  84. H. Sharghi, M. Hosseini-Sarvari, F. Moeini, Can. J. Chem. 86, 1044 (2008)

    Article  CAS  Google Scholar 

  85. H. Sharghi, M. Jokar, Heterocycles 71, 2721 (2007)

    Article  CAS  Google Scholar 

  86. H. Sharghi, A.R. Salimi-Beni, R. Khalifeh, Helv. Chim. Acta 90, 1373 (2007)

    Article  CAS  Google Scholar 

  87. H. Sharghi, A.R. Salimi-Beni, ARKIVOC xiii, 1 (2007)

    Google Scholar 

  88. A. Zare, A. Hasaninejad, M.H. Beyzavi, A. Parhami, A.R. Zare, M.A. Khalafi-Nezhad, H. Sharghi, Can. J. Chem. 86, 317 (2008)

    Article  CAS  Google Scholar 

  89. H. Sharghi, R. Khalifeh, Can. J. Chem. 86, 426 (2008)

    Article  CAS  Google Scholar 

  90. H. Sharghi, M. Jokar, M.M. Doroodmand, R. Khalifeh, Adv. Synth. Catal. 352, 3031 (2010)

    Article  CAS  Google Scholar 

  91. H. Sharghi, M. Jokar, M.M. Doroodmand, Adv. Synth. Catal. 353, 426 (2011)

    Article  CAS  Google Scholar 

  92. H. Sharghi, R. Khalifeh, Heterocycles 71, 1601 (2007)

    Article  CAS  Google Scholar 

  93. H. Firouzabadi, N. Iranpoor, A. Khoshnood, J. Mol. Catal. A 274, 109 (2007)

    Article  CAS  Google Scholar 

  94. A. Khalafi-Nezhad, M. N. Soltani Rad, A. Khoshnood. Synthesis 16, 2552 (2003)

    Google Scholar 

  95. A. Khalafi-Nezhad, M. N. Soltani Rad, A. Khoshnood. Synthesis 4, 583 (2004)

    Google Scholar 

  96. A. Brik, J. Alexandratos, Y.-C. Lin, J.H. Elder, A.J. Olson, A. Wlodawer, D.S. Goodsell, C.H. Wong, Chem. Biol. Chem. 6, 1167 (2005)

    CAS  Google Scholar 

  97. K.R. Reddy, C.U. Maheswari, K. Rajgopal, M.L. Kantam, Synth. Commun. 38, 2158 (2008)

    Article  CAS  Google Scholar 

  98. H. Sharghi, M. Hosseini-Sarvari, F. Moeini, R. Khalifeh, A.R. Salimi-Beni, Helv. Chim. Acta. 93, 435 (2010)

    Article  CAS  Google Scholar 

  99. H. Firouzabadi, N. Iranpoor, A. Garzan, Adv. Synth. Catal. 347, 1925 (2005)

    Article  CAS  Google Scholar 

  100. H. Firouzabadi, N. Iranpoor, M. Abbasi, Adv. Synth. Catal. 351, 755 (2009)

    Article  CAS  Google Scholar 

  101. H. Firouzabadi, N. Iranpoor, A.A. Jafari, E. Riazymontazer, Adv. Synth. Catal. 348, 434 (2006)

    Article  CAS  Google Scholar 

  102. H. Firouzabadi, N. Iranpoor, A. Khoshnood, Catal. Commun. 9, 529 (2008)

    Article  CAS  Google Scholar 

  103. F. Cozzi, Adv. Synth. Catal. 348, 1367 (2006) (see the references cited therein)

    Google Scholar 

  104. K. Binnemans, Chem. Rev. 109, 4283 (2009)

    Article  CAS  Google Scholar 

  105. C. Baleizão, H. Garcia, Chem. Rev. 106, 3987 (2006) (see the references cited therein)

  106. A.F. Trindade, P.M.P. Gois, C.A.M. Afonso, Chem. Rev. 109, 418 (2009) (see the references cited therein)

  107. J.M. Fraile, J.I. García, J.A. Mayoral, Chem. Rev. 109, 360 (2009)

    Article  CAS  Google Scholar 

  108. A.P. Wight, M.E. Davis, Chem. Rev. 102, 3589 (2002)

    Article  CAS  Google Scholar 

  109. L. Yin, J. Liebscher, Chem. Rev. 107, 133 (2007)

    Article  CAS  Google Scholar 

  110. A. Corma, H. Garcia, Adv. Synth. Catal. 348, 1391 (2006) (see the references cited therein)

    Google Scholar 

  111. S. Minakata, M. Komatsu, Chem. Rev. 109, 711 (2009) (see the references cited therein)

  112. C.A. McNamara, M.J. Dixon, M. Bradley. Chem. Rev. 102, 3275 (2002) (see the references cited therein)

    Google Scholar 

  113. H. Bloom, L.H. Briggs, B. Cleverley, J. Chem. Soc. 178, 178 (1959)

    Article  Google Scholar 

  114. H. Sharghi, R. Khalifeh, M.M. Doroodmand, Adv. Synth. Catal. 351, 207 (2009)

    Article  CAS  Google Scholar 

  115. J.W. Daly, W.L. Padgett, M.T. Shamim, J. Med. Chem. 29, 1305 (1986)

    Article  CAS  Google Scholar 

  116. A. Casaschi, R. Grigg, J.M. Sansano, Tetrahedron 56, 7553 (2000)

    Article  CAS  Google Scholar 

  117. M. Mabrour, K. Bougrin, R. Benhida, A. Loupyc, M. Soufiaouia, Tetrahedron Lett. 48, 443 (2007)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We appreciate the funding from Shiraz University research council for the financial support in work. We are grateful to Dr. M. Nakoei and Mr. M. Sorouri for their helps and comments during the progress of this work. We are also thankful to Mr. M.S. Darvish Tafvizi and Mr. H. Sajedian Fard for running the NMR and mass spectra.

Author information

Authors and Affiliations

  1. Department of Chemistry, College of Sciences, Shiraz University, 71454, Shiraz, Iran

    Hashem Sharghi, Abbas Khoshnood & Mohammad Mahdi Doroodmand

  2. Nanotechnology Research Institute, Shiraz University, Shiraz, Iran

    Mohammad Mahdi Doroodmand

  3. Department of Chemistry, Shiraz University of Technology, 71555-313, Shiraz, Iran

    Reza Khalifeh

Authors
  1. Hashem Sharghi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Abbas Khoshnood
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mohammad Mahdi Doroodmand
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Reza Khalifeh
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hashem Sharghi.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary Material 1 (DOC 6517 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sharghi, H., Khoshnood, A., Doroodmand, M.M. et al. 1,4-Dihydroxyanthraquinone-copper(II) nanoparticles immobilized on silica gel: a highly efficient, copper scavenger and recyclable heterogeneous nanocatalyst for a click approach to the three-component synthesis of 1,2,3-triazole derivatives in water. J IRAN CHEM SOC 9, 231–250 (2012). https://doi.org/10.1007/s13738-011-0046-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13738-011-0046-3

Keywords

Search

Navigation