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One-pot nitrodebromination and methyl bi-functionalization of 5-bromo 6-methylpyrimidines: a unique simultaneous transformation

Abstract

A unique one-pot, simultaneous nitrodebromination and methyl bromonitration occurred upon treatment of 5-bromo-2,4-di-tert-amino-6-methylpyrimidine derivatives with a cold mixture of concentrated H2SO4–HNO3 in moderate yields. It is actually a facile and rapid transformation that has been reported neither on pyrimidines nor simultaneously on other organic compounds.

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References

  1. Heravi MM, Zadsirjan V, Malmir M (2018) Molecules 23:943

    Article  CAS  Google Scholar 

  2. Heravi MM, Zadsirjan V, Hamidi H, Hajiabbas TAP (2017) RSC Adv 7:24470

    Article  Google Scholar 

  3. Heravi MM, Lashaki BT, Poorahmad N (2015) Tetrahedron: Asymmetry 26:405

  4. Ono N (2001) The nitro group in organic synthesis. Wiley-VCH, New York

    Book  Google Scholar 

  5. Soengas RG, Acurcio RC, Silva AM (2014) Eur J Org Chem 2014:6339

    CAS  Article  Google Scholar 

  6. Hernandes MZ, Cavalcanti SMT, Moreira DRM, de Azevedo J, Filgueira W, Leite ACL (2010) Curr Drug Targets 11:303

    CAS  PubMed  Article  Google Scholar 

  7. Sen S, Kamm SR, Potti VR, Murthy YLN, Chaudhary AB (2011) Tetrahedron Lett 52:5585

    CAS  Article  Google Scholar 

  8. Butler P, Golding BT, Laval G, Loghmani-Khouzani H, Ranjbar-Karimi R, Sadeghi MM (2007) Tetrahedron 63:11160

    CAS  Article  Google Scholar 

  9. Feuer H, Lawrence JP (1972) J Org Chem 37:3662

    CAS  Article  Google Scholar 

  10. Wu D, Zhang J, Cui J, Zhang W, Liu Y (2014) Chem Commun 50:10857

    CAS  Article  Google Scholar 

  11. Kurfürst A, Schwarz M (1989) Collect Czech Chem Commun 54:1346

    Article  Google Scholar 

  12. Kurfürst A, Raclová F, Kuthan J (1980) Collect Czech Chem Commun 45:397

    Article  Google Scholar 

  13. Stock NS, Bain G, Zunic J, Li Y, Ziff J, Roppe J, Santini A, Darlington J, Prodanovich P, King CD, Baccei C (2011) J Med Chem 54:8013

    CAS  PubMed  Article  Google Scholar 

  14. Su N, Bradshaw JS, Zhang XX, Song H, Savage PB, Xue G, Krakowiak KE, Izatt RM (1999) J Org Chem 64:8855

    CAS  PubMed  Article  Google Scholar 

  15. Adhikari S, Mandal S, Ghosh A, Das P, Das D (2015) J Org Chem 80:8530

    CAS  PubMed  Article  Google Scholar 

  16. Maj AM, Suisse I, Hardouin C, Agbossou-Niedercorn F (2013) Tetrahedron 69:9322

    CAS  Article  Google Scholar 

  17. Wang L, Hou X, Fu H, Pan X, Xu W, Tang W, Fang H (2015) Bioorg Med Chem 23:4364

    CAS  PubMed  Article  Google Scholar 

  18. Shults MD, Imperiali B (2003) J Am Chem Soc 125:14248

    CAS  PubMed  Article  Google Scholar 

  19. Bi WZ, Qu C, Chen XL, Wei SK, Qu LB, Liu SY, Sun K, Zhao YF (2018) Tetrahedron 74:1908

    CAS  Article  Google Scholar 

  20. Xie Y, Li L (2014) Tetrahedron Lett 55:3892

    CAS  Article  Google Scholar 

  21. Priyadarshini S, Joseph PA, Kantam ML, Sreedhar B (2013) Tetrahedron 69:6409

    CAS  Article  Google Scholar 

  22. Ravi P, Tewari SP (2013) Catal Commun 42:35

    CAS  Article  Google Scholar 

  23. Paik SU, Jung MG (2012) Bull Korean Chem Soc 33:689

    CAS  Article  Google Scholar 

  24. Ravi P, Gore GM, Sikder AK, Tewari SP (2012) Synth Commun 42:3463

    CAS  Article  Google Scholar 

  25. Wu X, Dube MA, Fry AJ (2006) Tetrahedron Lett 47:7667

    CAS  Article  Google Scholar 

  26. Chang K, Grimmett MR, Ward DD, Weavers RT (1979) Aust J Chem 32:1727

    CAS  Article  Google Scholar 

  27. Clewley RG, Fischer A, Henderson GN (1989) Can J Chem 67:1472

    CAS  Article  Google Scholar 

  28. Reznikov VA, Vishnivetskaya LA, Volodarsky LB (1994) Russ Chem Bull 43:275

    Article  Google Scholar 

  29. Russell G, Dedolph D (1985) J Org Chem 50:2498

    CAS  Article  Google Scholar 

  30. Feuer H, Friedman H (1975) J Org Chem 40:187

    CAS  Article  Google Scholar 

  31. Feuer H, Vincent EF (1964) J Org Chem 29:939

    CAS  Article  Google Scholar 

  32. Terentev AO, Krylov IB, Ogibin YN (2006) Synthesis 2006:3819

    Article  CAS  Google Scholar 

  33. Marchand AP, Arney BE Jr, Dave PR (1988) J Org Chem 53:443

    CAS  Article  Google Scholar 

  34. Mousavi M, Bakavoli M, Shiri A, Eshghi H (2018) ACS Sustainable Chem Eng 6:5852

    CAS  Article  Google Scholar 

  35. Heravi MM, Benmorad T, Bakhtiari Kh, Bamoharram FF, Oskooie H (2007) J Mol Catal A-Chem 264:318

    CAS  Article  Google Scholar 

  36. Heravi MM, Abdolhosseini N, Oskooie H (2005) Tetrahedron Lett 46:8959

    CAS  Article  Google Scholar 

  37. Bakavoli M, Rahimizadeh M, Shiri A, Eshghi H, Vaziri-Mehr S, Pordeli P, Nikpour M (2011) Heterocycl Commun 17:49

    CAS  Google Scholar 

  38. Eshghi H, Rahimizadeh M, Saberi S, Abnous K, Bakavoli M (2013) J Chem Res 37:553

    CAS  Article  Google Scholar 

  39. Bazazan T, Bakavoli M, Rahimizadeh M, Eshghi H, Nikpour M (2013) Heterocycl Commun 19:401

    CAS  Article  Google Scholar 

  40. Ebrahimpour Z, Shiri A, Bakavoli M, Seyedi SM, Asghari T, Mague J (2017) J Heterocycl Chem 54:235

    CAS  Article  Google Scholar 

  41. Igei M, Bakavoli M, Shiri A, Ebrahimpour Z, Azizollahi H, Beyzaei H, Moghaddam-Manesh M (2016) J Chem Res 40:628

    CAS  Article  Google Scholar 

  42. Mousavi M, Bakavoli M, Shiri A, Tajabadi J (2018) Chemistry Select 3:5401

    Google Scholar 

  43. Tajabadi J, Bakavoli M, Gholizadeh M, Eshghi H, Izadyar M (2015) RSC Adv 5:38489

    CAS  Article  Google Scholar 

  44. Bakavoli M, Eshghi H, Shiri A, Afrough T, Tajabadi J (2013) Tetrahedron 69:8470

    CAS  Article  Google Scholar 

  45. Lodewyk MW, Siebert MR, Tantillo DJ (2012) Chem Rev 112:1839

    CAS  PubMed  Article  Google Scholar 

  46. Minkin VI, Mikhailov IE, Dushenko GA, Yudilevich JA, Minyaev RM, Zschunke A, Mögge K (1991) J Phys Org Chem 4:31

    CAS  Article  Google Scholar 

  47. Ditchfield R (1974) Mol Phys 27:789

    CAS  Article  Google Scholar 

  48. Sarotti AM, Pellegrinet SCA (2009) J Org Chem 74:7254

    CAS  PubMed  Article  Google Scholar 

  49. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb, MA, Cheeseman JR, Scalmani G, Barone V, Mennucci, B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision A.02. Gaussian, Inc, Wallingford, CT

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Acknowledgements

M. M. acknowledges the Research Council of Ferdowsi University of Mashhad for partial support of this project (3/33579). M. M. H. is grateful to Alzahra University Research Council as well as appreciates the granted research chair by Iran National Science Foundation (INSF).

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Correspondence to Mahsa Mousavi or Majid M. Heravi.

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In memory of professor Mehdi Bakavoli, who was skilled, mastered, and proficient at pyrimidine chemistry.

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Mousavi, M., Heravi, M.M. & Tajabadi, J. One-pot nitrodebromination and methyl bi-functionalization of 5-bromo 6-methylpyrimidines: a unique simultaneous transformation. Monatsh Chem 151, 1395–1401 (2020). https://doi.org/10.1007/s00706-020-02658-7

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  • DOI: https://doi.org/10.1007/s00706-020-02658-7

Keywords

  • Gem-bromonitromethyl pyrimidine
  • Bromonitration
  • Nitrodebromination
  • Additive free
  • Catalyst free