Skip to main content
SpringerLink
Log in

Sodium ascorbate as an expedient catalyst for green synthesis of polysubstituted 5-aminopyrazole-4-carbonitriles and 6-amino-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles

  • Published:
Research on Chemical Intermediates Aims and scope Submit manuscript

Abstract

Sodium ascorbate (SA) was used as a safe catalyst for the synthesis of 5-aminopyrazole-4-carbonitriles from the one-pot three-component cyclocondensation (3-CC) of aldehydes, phenylhydrazine, and malononitrile at 50 °C. This 3-CC proceeds in a mixture of ethanol–water as a green reaction medium to give the desired densely functionalized pyrazoles in good to high yields. 6-Amino-1,4-dihydropyrano-[2,3-c]pyrazole-5-carbonitriles were also synthesized in the presence of SA via an eco-friendly and simple four-component cyclocondensation (4-CC). This 4-CC performed in refluxing water as a green medium and dihydropyrano-[2,3-c]pyrazole products were obtained in excellent yields and relatively shorter reaction times. These environmentally friendly multicomponent cyclocondensations offer some interesting advantages, including time-saving, easily available starting materials, mild conditions, minimizing the amount of waste, good atom efficiency, avoiding hazardous organic solvents or catalysts, and the ease of the work-up.

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

Similar content being viewed by others

References

  1. S. Chauhan, S. Paliwal, R. Chauhan, Synth. Commun. 44, 1333 (2014)

    Article  Google Scholar 

  2. S. Kumari, S. Paliwal, R. Chauhan, Synth. Commun. 44, 1521 (2014)

    Article  CAS  Google Scholar 

  3. M.F. Khan, M.M. Alam, G. Verma, W. Akhtar, M. Akhter, M. Shaquiquzzaman, Eur. J. Med. Chem. 120, 170 (2016)

    Article  CAS  Google Scholar 

  4. A.A. Bekhita, T. Abdel-Aziem, Bioorg. Med. Chem. 12, 1935 (2004)

    Article  Google Scholar 

  5. F.A. Ragab, N.M. Abdel Gawad, H.H. Georgey, M.F. Said, Eur. J. Med. Chem. 63, 645 (2013)

    Article  CAS  Google Scholar 

  6. K.S. Mohamed, A.A. Fadda, Heterocycles 91, 1937 (2015)

    Article  CAS  Google Scholar 

  7. R.S. Keri, K. Chand, T. Ramakrishnappa, B.M. Nagaraja, Arch. Pharm. Chem. Life Sci. 348, 1 (2015)

    Article  Google Scholar 

  8. H. Maruoka, M. Hokao, N. Kashige, E. Masumoto, F. Okabe, R. Tanaka, F. Miake, T. Fujioka, K. Yamagata, Heterocycles 93, 362 (2016)

    Article  CAS  Google Scholar 

  9. Ş.G. Küçükgüzel, S. Şenkardeş, Eur. J. Med. Chem. 97, 786 (2015)

    Article  Google Scholar 

  10. A. Akbari, B.F. Mirjalili, Rev. Roum. Chim. 61, 119 (2016)

    Google Scholar 

  11. Z. Wu, S. Wu, Y. Ye, X. Zhou, P. Wang, W. Xue, D. Hu, J. Heterocycl. Chem. 54, 325 (2017)

    Article  CAS  Google Scholar 

  12. A.A. Bekhit, A.M.M. Hassan, H.A. Abd El Razik, M.M.M. El-Miligy, E.J. El-Agroudy, A.E.A. Bekhit, Eur. J. Med. Chem. 94, 30 (2015)

    Article  CAS  Google Scholar 

  13. F.P.L. Lim, G. Luna, A.V. Dolzhenko, Synthesis 48, 2423 (2016)

    Article  CAS  Google Scholar 

  14. M.D. Hill, Synthesis 48, 2201 (2016)

    Article  CAS  Google Scholar 

  15. H. Raju, S. Chandrappa, D.S. Prasanna, H. Ananda, T.S. Nagamani, S.M. Byregowda, K.S. Rangappa, Recent Pat. Anticancer Drug Discov. 6, 186 (2011)

    Article  CAS  Google Scholar 

  16. T. Liu, R. Cui, J. Chen, J. Zhang, Q. He, B. Yang, Y. Hu, Arch. Pharm. Chem. Life Sci. 11, 279 (2011)

    Article  Google Scholar 

  17. M. Srivastava, P. Rai, J. Singh, J. Singh, RSC Adv. 3, 16994 (2013)

    Article  CAS  Google Scholar 

  18. M. Srivastava, P. Rai, J. Singh, J. Singh, New J. Chem. 38, 302 (2014)

    Article  CAS  Google Scholar 

  19. P. Rai, M. Srivastava, J. Singh, J. Singh, RSC Adv. 4, 779 (2014)

    Article  CAS  Google Scholar 

  20. M. Mahdavi, M. Khoshbakht, M. Saeedi, M. Asadi, M. Bayat, A. Foroumadi, A. Shafiee, Synthesis 48, 541 (2016)

    Article  CAS  Google Scholar 

  21. A. Kamal, K.N. Visweswara Sastry, D. Chandrasekhar, G.S. Mani, P.R. Adiyala, J.B. Nanubolu, K.K. Singarapu, R.A. Maurya, J. Org. Chem. 80, 4325 (2015)

    Article  CAS  Google Scholar 

  22. B. Chen, C. Zhu, Y. Tanga, S. Ma, Chem. Commun. 50, 7677 (2014)

    Article  CAS  Google Scholar 

  23. D.Y. Li, X.F. Mao, H.J. Chen, G.R. Chen, P.N. Liu, Org. Lett. 16, 3476 (2014)

    Article  CAS  Google Scholar 

  24. S. Kumari, A. Shekhar, D.D. Pathak, New J. Chem. 40, 5053 (2016)

    Article  CAS  Google Scholar 

  25. M. Kashiwa, Y. Kuwata, M. Sonoda, S. Tanimori, Tetrahedron 72, 304 (2016)

    Article  CAS  Google Scholar 

  26. S. Maddila, S. Rana, R. Pagadala, S. Kankala, S. Maddila, S.B. Jonnalagadda, Catal. Commun. 61, 26 (2015)

    Article  CAS  Google Scholar 

  27. A. Saeed, P.A. Channar, J. Heterocycl. Chem. 54, 780 (2017)

    Article  CAS  Google Scholar 

  28. S. Yadav, P. Rai, M. Srivastava, J. Singh, K.P. Tiwari, J. Singh, Tetrahedron Lett. 56, 5831 (2015)

    Article  CAS  Google Scholar 

  29. M.A. Zolfigol, F. Afsharnadery, S. Baghery, S. Salehzadeh, F. Maleki, RSC Adv. 5, 7555 (2015)

    Google Scholar 

  30. F.J. Meng, T. Sun, W.Z. Dong, M.H. Li, Z.Z. Tuo, Arch. Pharm. Chem. Life Sci. 349, 168 (2016)

    Article  CAS  Google Scholar 

  31. V.J. Dhanaji, R.P. Umesh, R.M. Jyotirling, A.M. Ramrao, Chin. Chem. Lett. 22, 1187 (2011)

    Google Scholar 

  32. M. Ubale, M. Shioorkar, Heterocycl. Lett. 6, 365 (2016)

    CAS  Google Scholar 

  33. L. Shen, S. Cao, L. Nianjin, J. Wu, L. Zhu, X. Qian, Synlett 2008, 1341 (2008)

    Article  Google Scholar 

  34. C. Ma, P. Wen, J. Li, X. Han, Z. Wu, G. Huang, Adv. Synth. Catal. 358, 1073 (2016)

    Article  CAS  Google Scholar 

  35. D.H. Oliveira, T.B. Aquino, J.E.R. Nascimento, G. Perin, R.G. Jacob, D. Alves, Adv. Synth. Catal. 357, 4041 (2015)

    Article  CAS  Google Scholar 

  36. R.P. Pandit, Y.R. Lee, Adv. Synth. Catal. 357, 2657 (2015)

    Article  CAS  Google Scholar 

  37. F. Nemati, S.H. Nikkhah, A. Elhampour, Chin. Chem. Lett. 26, 1397 (2015)

    Article  CAS  Google Scholar 

  38. A.A. Fadda, A. El-Mekabaty, K.M. Elattar, Synth. Commun. 43, 2685 (2013)

    Article  CAS  Google Scholar 

  39. B. Myrboh, H. Mecadon, M.R. Rohman, M. Rajbangshi, I. Kharkongor, B.M. Laloo, I. Kharbangar, B. Kshiar, Org. Prep. Proced. Int. 45, 253 (2013)

    Article  CAS  Google Scholar 

  40. A. Sharma, B. Pallavi, R.P. Singh, P.N. Jha, P. Shukla, Heterocycles 91, 1615 (2015)

    Article  CAS  Google Scholar 

  41. Y.A. Tayade, S.A. Padvi, Y.B. Wagh, D.S. Dalal, Tetrahedron Lett. 56, 2441 (2015)

    Article  CAS  Google Scholar 

  42. F. Tamaddon, M.A. Alizadeh, Tetrahedron Lett. 55, 3588 (2014)

    Article  CAS  Google Scholar 

  43. P.P. Bora, M. Bihani, G. Bez, J. Mol. Catal. B Enzym. 92, 24 (2013)

    Article  CAS  Google Scholar 

  44. G. Brahmachari, B. Banerjee, A.C.S. Sustain, Chem. Eng. 2, 411 (2014)

    CAS  Google Scholar 

  45. A. Saha, S. Payra, S. Banerjee, Green Chem. 17, 2859 (2015)

    Article  CAS  Google Scholar 

  46. M. Wu, Q. Feng, D. Wan, J. Ma, Synth. Commun. 43, 1721 (2013)

    Article  CAS  Google Scholar 

  47. A.I. Ilovaisky, M.G. Medvedev, V.M. Merkulova, M.N. Elinson, G.I. Nikishin, J. Heterocycl. Chem. 51, 523 (2014)

    Article  CAS  Google Scholar 

  48. J. Albadi, A. Mansournezhad, F. Akbari, Blout-Bangan. Acta Chim. Slov. 61, 190 (2014)

    Google Scholar 

  49. R.Y. Guo, Z.M. An, L.P. Mo, S.T. Yang, H.X. Liu, S.X. Wang, Z.H. Zhang, Tetrahedron 69, 9931 (2013)

    Article  CAS  Google Scholar 

  50. G.S. Kumar, C. Kurumurthy, B. Veeraswamy, P.S. Rao, P.S. Rao, B. Narsaiah, Org. Prep. Proced. Int. 45, 429 (2013)

    Article  CAS  Google Scholar 

  51. K. Niknam, N. Borazjani, R. Rashidian, A. Jamali, Chin. J. Catal. 34, 2245 (2013)

    Article  CAS  Google Scholar 

  52. J.M. Khurana, K. Vij, Synth. Commun. 43, 2294 (2013)

    Article  CAS  Google Scholar 

  53. M.A. Chaudhari, J.B. Gujar, D.S. Kawade, M.S. Shingare, Chem. Biol. Interface 5, 44 (2015)

    Google Scholar 

  54. K. Eskandari, B. Karami, S. Khodabakhshi, Catal. Commun. 54, 124 (2014)

    Article  CAS  Google Scholar 

  55. M.N. Elinson, R.F. Nasybullin, F.V. Ryzhkov, T.A. Zaimovskaya, G.I. Nikishin, Monatsh. Chem. 146, 631 (2015)

    Article  CAS  Google Scholar 

  56. F. Boukezzoula, T. Boumoud, B. Boumoud, A. Debache, Chem. Sci. Trans. 4, 611 (2015)

    CAS  Google Scholar 

  57. M. Parshad, V. Verma, D. Kumar, Monatsh. Chem. 145, 1857 (2014)

    Article  CAS  Google Scholar 

  58. M. Farahi, B. Karami, I. Sedighimehr, H.M. Tanuraghaj, Chin. Chem. Lett. 25, 1580 (2014)

    Article  CAS  Google Scholar 

  59. J.B. Gujar, M.A. Chaudhari, D.S. Kawade, M.S. Shingare, Tetrahedron Lett. 55, 6030 (2014)

    Article  CAS  Google Scholar 

  60. M.A. Zolfigol, M. Tavasoli, A.R. Moosavi-Zare, P. Moosavi, H.G. Kruger, M. Shiri, V. Khakyzadeh, RSC Adv. 3, 25681 (2013)

    Article  CAS  Google Scholar 

  61. A.S. Waghmare, S.S. Pandit, J. Saudi Chem. Soc. 21, 286 (2017)

    Article  CAS  Google Scholar 

  62. K. Ablajan, W. Liju, A. Tuoheti, Y. Kelimu, Lett. Org. Chem. 9, 639 (2012)

    Article  CAS  Google Scholar 

  63. R.H. Vekariya, K.D. Patel, H.D. Patel, Res. Chem. Intermed. 42, 4683 (2016)

    Article  CAS  Google Scholar 

  64. M.A. Chaudhari, J.B. Gujar, D.S. Kawade, N.R. Jogdand, M.S. Shingare, Cogent Chem. 1, 1063830 (2015)

    Google Scholar 

  65. A.K. Imène, G. Wassima, B. Raouf, B. Taous, D. Abdelmadjid, Der Pharma Chem. 7, 175 (2015)

    Google Scholar 

  66. R.H. Vekariya, K.D. Patel, H.D. Patel, Iran. J. Org. Chem. 7, 1581 (2015)

    Google Scholar 

  67. H. Kiyani, H.A. Samimi, F. Ghorbani, S. Esmaieli, Curr. Chem. Lett. 2, 197 (2013)

    Article  CAS  Google Scholar 

  68. R.H. Vekariya, K.D. Patel, H.D. Patel, Res. Chem. Intermed. 42, 7559 (2016)

    Article  CAS  Google Scholar 

  69. R.C. Cioc, E. Ruijter, R.V.A. Orru, Green Chem. 16, 2958 (2014)

    Article  CAS  Google Scholar 

  70. S. Garbarino, D. Ravelli, S. Protti, A. Basso, Angew. Chem. Int. Ed. 55, 25476 (2016)

    Article  Google Scholar 

  71. H. Kiyani, F. Ghorbani, J. Saudi Chem. Soc. 18, 689 (2014)

    Article  Google Scholar 

  72. H. Kiyani, F. Ghorbani, J. Saudi Chem. Soc. 21, S112 (2017)

    Article  CAS  Google Scholar 

  73. H. Kiyani, S. Aslanpour, Heterocycles 94, 1314 (2017)

    Article  CAS  Google Scholar 

  74. H. Kiyani, M. Bamdad, Heterocycles 94, 276 (2017)

    Article  Google Scholar 

  75. H. Kiyani, M. Bamdad, Rev. Roum. Chim. 62, 221 (2017)

    Google Scholar 

  76. H. Kiyani, M.S. Jalali, Heterocycles 92, 75 (2016)

    Article  CAS  Google Scholar 

  77. H. Kiyani, M.S. Jalali, Comb. Chem. High Throughput Screen. 19, 275 (2016)

    Article  CAS  Google Scholar 

  78. H. Kiyani, M. Tazari, Res. Chem. Intermed. 43, 6639 (2017)

    Article  CAS  Google Scholar 

  79. M. Gupta, M. Gupta, V.K.Gupta Rajnikant, New J. Chem. 39, 3578 (2015)

    Article  CAS  Google Scholar 

  80. S.S. Mansoor, K. Logaiya, K. Aswin, P.N. Sudhan, J. Taibah Univ. Sci. 9, 213 (2015)

    Article  Google Scholar 

  81. A. Berardo, H. De Maere, D.A. Stavropoulou, T. Rysman, F. Leroy, S. De Smet, Meat Sci. 121, 359 (2016)

    Article  CAS  Google Scholar 

  82. C. Celik, S. Erkut, K. Gulsahi, K. Yamanel, C. Kucukesmen, Aust. Endod. J. 36, 12 (2010)

    Article  Google Scholar 

  83. B.V.A. Rao, S.S. Rao, Mater. Corros. 61, 285 (2010)

    CAS  Google Scholar 

  84. T. Rysman, T.V. Hecke, S. De Smet, G.V. Royen, J. Agric. Food Chem. 64, 4131 (2016)

    Article  CAS  Google Scholar 

  85. H. Kiyani, F. Ghorbani, Jordan J. Chem. 8, 191 (2013)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  87. W.H. Binder, R. Sachsenhofer, Macromol. Rapid Commun. 28, 15 (2007)

    Article  CAS  Google Scholar 

  88. A. Qin, J.W.Y. Lam, B.Z. Tang, Chem. Soc. Rev. 39, 2522 (2010)

    Article  CAS  Google Scholar 

  89. D.V. Vorobyeva, N.M. Karimova, I.L. Odinets, G.V. Roschenthaler, S.N. Osipov, Org. Biomol. Chem. 9, 7335 (2011)

    Article  CAS  Google Scholar 

  90. H. Kiyani, Org. Chem. Indian J. 9, 97 (2013)

    CAS  Google Scholar 

  91. A. Rotaru, S. Dutta, E. Jentzsch, K. Gothelf, A. Mokhir, Angew. Chem. Int. Ed. 49, 5665 (2010)

    Article  CAS  Google Scholar 

  92. Z. Qing, X. He, D. He, K. Wang, F. Xu, T. Qing, X. Yang, Angew. Chem. Int. Ed. 52, 9719 (2013)

    Article  CAS  Google Scholar 

  93. H.B. Wang, H.D. Zhang, Y. Chen, L.J. Ou, Y.M. Liu, Anal. Methods 7, 6372 (2015)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The Damghan University is acknowledged for the provision of facilities.

Author information

Authors and Affiliations

  1. School of Chemistry, Damghan University, Damghan, 36716-41167, Iran

    Hamzeh Kiyani & Maryam Bamdad

Authors
  1. Hamzeh Kiyani
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Maryam Bamdad
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hamzeh Kiyani.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kiyani, H., Bamdad, M. Sodium ascorbate as an expedient catalyst for green synthesis of polysubstituted 5-aminopyrazole-4-carbonitriles and 6-amino-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles. Res Chem Intermed 44, 2761–2778 (2018). https://doi.org/10.1007/s11164-018-3260-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11164-018-3260-0

Keywords

Search

Navigation