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Design and synthesis of novel ditopic ligands with a pyrazole ring in the central unit

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Abstract

Four novel ditopic ligands that have a pyrazole ring in their central unit and are useful for the generation of coordination polymers have been synthesized. Two of these ditopic ligands present two carboxylate functions as coordinating groups, while the other two are hybrid ligands having only one carboxylate function and either tetrazolate or imidazole as the remaining coordination site. The ligands have been obtained through a multi-step reaction sequence that begins with the Claisen condensation of either 4-acetylbenzonitrile or 4-(1H-imidazol-1-yl)acetophenone with diethyl oxalate and has the Knorr pyrazole ring closure as its key step. Subsequently, the tetrazolate in one of the ligands is constructed through a [3 + 2] cycloaddition of azide anion to the cyano group, while hydrolysis of the ester and the cyano substituents generates the carboxylate function(s). The structure of the intermediates and of the target ligands has been investigated by solution NMR, special attention being given to keto–enol and pyrazole tautomerism when present. The structure of two ligands and a key intermediate has also been established by single-crystal X-ray diffraction.

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References

  1. Y. Lin, C. Kong, Q. Zhang, L. Chen, Adv. Energy Mater. 7, 1601296 (2017)

    Article  CAS  Google Scholar 

  2. H. Li, K. Wang, Y. Sun, C.T. Lollar, J. Li, H.-C. Zhou, Mater. Today 21, 108 (2018)

    Article  CAS  Google Scholar 

  3. X. Yang, Q. Xu, Cryst. Growth Des. 17, 1450 (2017)

    Article  CAS  Google Scholar 

  4. L. Zhu, X.-Q. Liu, H.-L. Jiang, L.-B. Sun, Chem. Rev. 117, 8129 (2017)

    Article  CAS  PubMed  Google Scholar 

  5. C. Janiak, J.K. Vieth, New J. Chem. 34, 2366 (2010)

    Article  CAS  Google Scholar 

  6. Z.-Q. Shi, Z.-J. Guo, H.-G. Zheng, Chem. Commun. 51, 8300 (2015)

    Article  CAS  Google Scholar 

  7. H. Erer, O.Z. Yeşilel, M. Arici, S. Keskin, O. Büyükgüngör, J. Solid State Chem. 210, 261 (2014)

    Article  CAS  Google Scholar 

  8. H.-H. Li, Z. Niu, L. Chen, H.-B. Jiang, Y.-P. Wang, P. Cheng, CrystEngComm 17, 5101 (2015)

    Article  CAS  Google Scholar 

  9. R. Sen, D. Mal, P. Brandão, G. Rogez, Z. Lin, CrystEngComm 15, 2113 (2013)

    Article  CAS  Google Scholar 

  10. S. Demir, H.M. Çepni, N. Bilgin, M. Hołyńska, F. Yilmaz, Polyhedron 115, 236 (2016)

    Article  CAS  Google Scholar 

  11. I. Voda, G. Makhloufi, V. Druta, V. Lozan, S. Shova, P. Bourosh, V. Kravtsov, C. Janiak, Inorg. Chim. Acta 482, 526 (2018)

    Article  CAS  Google Scholar 

  12. Y. Zhang, X. Luo, Z. Yang, G. Li, CrystEngComm 14, 7382 (2012)

    Article  CAS  Google Scholar 

  13. Z.-G. Gu, Y.-T. Liu, X.-J. Hong, Q.-G. Zhan, Z.-P. Zheng, S.-R. Zheng, W.-S. Li, S.-J. Hu, Y.-P. Cai, Cryst. Growth Des. 12, 2178 (2012)

    Article  CAS  Google Scholar 

  14. L. Bahrin, I. Rosca, L. Clima, S. Shova, D. Bejan, A. Nicolescu, N. Marangoci, M. Sardaru, V. Lozan, A. Rotaru, Inorg. Chem. Commun. 92, 60 (2018)

    Article  CAS  Google Scholar 

  15. D. Bejan, L.G. Bahrin, S. Shova, M. Sardaru, L. Clima, A. Nicolescu, N. Marangoci, V. Lozan, C. Janiak, Inorg. Chim. Acta 482, 275 (2018)

    Article  CAS  Google Scholar 

  16. I.-A. Dascalu, S. Shova, D.G. Dumitrescu, G. Roman, B.-I. Bratanovici, R. Ardeleanu, V. Lozan, Polyhedron 170, 463 (2019)

    Article  CAS  Google Scholar 

  17. L.G. Bahrin, D. Bejan, S. Shova, M. Gdaniec, M. Fronc, V. Lozan, C. Janiak, Polyhedron 173, 114128 (2019)

    Article  CAS  Google Scholar 

  18. Y.L. Janin, Mini Rev. Org. Chem. 7, 314 (2010)

    Article  CAS  Google Scholar 

  19. A.G. Waterson, J.P. Kennedy, J.D. Patrone, N.F. Pelz, M.D. Feldkamp, A.O. Frank, B. Vangamudi, E.M. Souza-Fagundes, O.W. Rossanese, W.J. Chazin, S.W. Fesik, ACS Med. Chem. Lett. 6, 140 (2015)

    Article  CAS  PubMed  Google Scholar 

  20. H.R. Hoveyda, M.-O. Roy, S. Blanc, S. Noël, J.M. Salvino, M.A. Ator, G. Fraser, Bioorg. Med. Chem. Lett. 21, 1991 (2011)

    Article  CAS  PubMed  Google Scholar 

  21. K. Tsuji, K. Nakamura, N. Konishi, T. Tojo, T. Ochi, H. Senoh, M. Matsuo, Chem. Pharm. Bull. 45, 987 (1997)

    Article  CAS  Google Scholar 

  22. T. Rogez-Florent, S. Meignan, C. Foulon, P. Six, A. Gros, C. Bal-Mahieu, C.T. Supuran, A. Scozzafava, R. Frédérick, B. Masereel, P. Depreux, A. Lansiaux, J.-F. Goossens, S. Gluszok, L. Goossens, Bioorg. Med. Chem. 21, 1451 (2013)

    Article  CAS  PubMed  Google Scholar 

  23. J.N. Spencer, E.S. Holmboe, M.R. Kirshenbaudm, D.W. Firth, P.B. Pinto, Can. J. Chem. 60, 1178 (1982)

    Article  CAS  Google Scholar 

  24. V.R. Darugar, M. Vakili, A.R. Nekoei, S.F. Tayyari, R. Afzali, J. Mol. Struct. 1150, 427 (2017)

    Article  CAS  Google Scholar 

  25. S.P. Singh, D. Kumar, H. Batra, R. Naithani, I. Rozas, J. Elguero, Can. J. Chem. 78, 1109 (2000). (References cited therein)

    Article  CAS  Google Scholar 

  26. T. Norris, R. Colon-Cruz, D.H.B. Ripin, Org. Biomol. Chem. 3, 1844 (2003)

    Article  CAS  Google Scholar 

  27. A.V. Zerov, T.S. Krupenya, A.A. Petrov, S.I. Yakimovich, Russ. J. Org. Chem. 52, 312 (2016)

    Article  CAS  Google Scholar 

  28. R.M. Claramunt, C. Lopez, M.D. Santa Maria, D. Sanz, J. Elguero, Prog. Nucl. Magn. Reson. Spectrosc. 49, 169 (2006)

    Article  CAS  Google Scholar 

  29. D. Sanz, R.M. Claramunt, I. Alkorta, J. Elguero, W.R. Thiel, T. Ruffer, New J. Chem. 32, 2225 (2008)

    Article  CAS  Google Scholar 

  30. E.D. Doidge, J.W. Roebuck, M.R. Healy, P.A. Tasker, Coord. Chem. Rev. 288, 98 (2015)

    Article  CAS  Google Scholar 

  31. J. Klingele, S. Dechert, F. Meyer, Coord. Chem. Rev. 253, 2698 (2009)

    Article  CAS  Google Scholar 

  32. C. Pettinari, A. Tăbăcaru, S. Galli, Coord. Chem. Rev. 307, 1 (2016)

    Article  CAS  Google Scholar 

  33. W.V. Murray, M.P. Wachter, J. Heterocycl. Chem. 26, 1389 (1989)

    Article  CAS  Google Scholar 

  34. M.A. Tabrizi, P.G. Baraldi, E. Ruggiero, G. Saponaro, S. Baraldi, R. Romagnoli, A. Martinelli, T. Tuccinardi, Eur. J. Med. Chem. 97, 289 (2015)

    Article  CAS  Google Scholar 

  35. M. Alvarado, J. Decara, M.J. Luque, L. Hernandez-Folgado, M. Gómez-Cañas, M. Gómez-Ruiz, J. Fernández-Ruiz, J. Elguero, N. Jagerovic, A. Serrano, P. Goya, F. Rodríguez de Fonseca, Bioorg. Med. Chem. 21, 1708 (2013)

    Article  CAS  PubMed  Google Scholar 

  36. I. Alkorta, M. Alvarado, J. Elguero, S. García-Granda, P. Goya, L. Torre-Fernández, L. Menéndez-Taboada, J. Mol. Struct. 920, 82 (2009)

    Article  CAS  Google Scholar 

  37. A.P. Kozikowski, S. Tapadar, D.N. Luchini, K.H. Kim, D.D. Billadeau, J. Med. Chem. 51, 4370 (2008)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  38. K. Liu, Y. Peng, F. Yang, D. Ma, G. Li, Z. Shi, S. Feng, CrystEngComm 16, 4382 (2014)

    Article  CAS  Google Scholar 

  39. S.-J. Bao, R. Krishna, Y.-B. He, J.-S. Qin, Z.-M. Su, S.-L. Li, W. Xie, D.-Y. Du, W.-W. He, S.-R. Zhang, Y.-Q. Lan, J. Mater. Chem. A 3, 7361 (2015)

    Article  CAS  Google Scholar 

  40. Y.-P. Xu, Y.-H. Chen, Z.-J. Chen, J. Qin, S.-S. Qian, H.-L. Zhu, Eur. J. Inorg. Chem. 2015, 2076 (2015)

    Article  CAS  Google Scholar 

  41. Y.-H. Mu, Z.-W. Ge, C.-P. Li, Inorg. Chem. Commun. 48, 94 (2014)

    Article  CAS  Google Scholar 

  42. C. Heering, I. Boldog, V. Vasylyeva, J. Sanchiz, C. Janiak, CrystEngComm 15, 9757 (2013)

    Article  CAS  Google Scholar 

  43. Y. Zhou, R. Ni, G. Yang, Synth. Commun. 40, 2624 (2010)

    Article  CAS  Google Scholar 

  44. V.I. Minkin, A.D. Garnovskii, J. Elguero, A.R. Katritzky, O.V. Denisko, Adv. Heterocycl. Chem. 76, 157 (2000)

    Article  CAS  Google Scholar 

  45. R. Ardeleanu, A. Dascălu, S. Shova, A. Nicolescu, I. Roşca, B.-I. Bratanovici, V. Lozan, G. Roman, J. Mol. Struct. 1173, 63 (2018)

    Article  CAS  Google Scholar 

  46. CrysAlisRED, Oxford Diffraction Ltd., Version 1.171.34.76 (2003)

  47. O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl. Cryst. 42, 339 (2009)

    Article  CAS  Google Scholar 

  48. G.M. Sheldrick, Acta Crystallogr. C 71, 3 (2015)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The financial support of European Social Fund for Regional Development, Competitiveness Operational Programme Axis 1—Project “Novel Porous Coordination Polymers with Organic Ligands of Variable Length for Gas Storage,” POCPOLIG (ID P_37_707, Contract 67/08.09.2016, cod MySMIS: 104810) is gratefully acknowledged.

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Authors and Affiliations

  1. Centre of Advanced Research in Bionanoconjugates and Biopolymers (IntelCentru), Petru Poni Institute of Macromolecular Chemistry, 41A Aleea Gr. Ghica Vodă, 700487, Iasi, Romania

    Bogdan-Ionel Bratanovici, Ioan-Andrei Dascălu & Vasile Lozan

  2. Faculty of Chemistry, Alexandru Ioan Cuza University, 11 Bd. Carol, 700506, Iasi, Romania

    Bogdan-Ionel Bratanovici

  3. Department of Physics of Polymers and Polymeric Materials, Petru Poni Institute of Macromolecular Chemistry, 41A Aleea Gr. Ghica Vodă, 700487, Iasi, Romania

    Alina Nicolescu

  4. Department of Inorganic Polymers, Petru Poni Institute of Macromolecular Chemistry, 41A Aleea Gr. Ghica Vodă, 700487, Iasi, Romania

    Sergiu Shova, Rodinel Ardeleanu & Gheorghe Roman

  5. Institute of Chemistry of MECR, 3 Academiei Str., 2028, Chişinău, Republic of Moldova

    Vasile Lozan

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  1. Bogdan-Ionel Bratanovici
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Bratanovici, BI., Nicolescu, A., Shova, S. et al. Design and synthesis of novel ditopic ligands with a pyrazole ring in the central unit. Res Chem Intermed 46, 1587–1611 (2020). https://doi.org/10.1007/s11164-019-04052-3

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