Skip to main content
SpringerLink
Log in

Sodium dichloroiodate promoted C-C bond cleavage: An efficient synthesis of 1,3-Benzazoles via condensation of \({\varvec{o}}\)-amino/mercaptan/hydroxyanilines with \({\varvec{\beta }}\)-diketones

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

An efficient aqueous sodium dichloroiodate (\(\hbox {NaICl}_{2})\) mediated protocol is developed for the synthesis of benzofused azoles by the cyclization of 2-amino anilines/thiophenols/phenols with \(\beta \)-diketone compounds. The reactions gave moderate to good yield of the corresponding 2-substituted benzimidazoles/benzothiazoles/benzoxazoles under mild conditions. This tandem process involved a C-C bond cleavage and C-N bond formation.

Graphical Abstract 

SYNOPSIS A facile and single protocol for the synthesis of three versatile 1,3-benzazoles viz 2-substituted 1H-benzimidazoles, benzoxazoles and benzothiazoles from readily available starting materials, 1,3-diketones and corresponding o-amino anilines/thiophenols/phenols, by aqueous sodium dichloroiodate (\(\hbox {NaICl}_{2})\) mediated C—C bond cleavage has been developed. The reaction provides a rapid access to these 1, 3-benzazoles in good yields, thus speeding up the drug discovery process.

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
Scheme 4
Scheme 5

Similar content being viewed by others

References

  1. Bansal Y and Silakari O 2012 The therapeutic journey of benzimidazoles: A review Bioorg. Med. Chem. 20 6208

    Article  CAS  Google Scholar 

  2. Keri R S, Patil M R, Patil S A and Budagumpi S 2015 A comprehensive review in current developments of benzothiazole-based molecules in medicinal chemistry Eur. J. Med. Chem. 89 207

    Article  CAS  Google Scholar 

  3. Tong Y S, Bouska J J, Ellis P A, Johnson E F, Leverson J, Liu X S, Marcotte P A, Olson A M, Osterling D J, Przytulinska M, Rodriguez L E, Shi Y, Soni N, Stavropoulos J, Thomas S, Donawho C K, Frost D J, Luo Y, Giranda V L and Penning T D 2009 Synthesis and evaluation of a new generation of orally efficacious benzimidazole-based poly(ADP-ribose) polymerase-1 (PARP-1) inhibitors as anticancer agents J. Med. Chem. 52 6803

    Article  CAS  Google Scholar 

  4. Achar K C S, Hosamani K M and Seetharamareddy H R 2010 In-vivo analgesic and anti-inflammatory activities of newly synthesized benzimidazole derivatives Eur. J. Med. Chem. 45 2048

    Article  CAS  Google Scholar 

  5. Ertan T, Yildiz I, Tekiner-Gulbas B, Bolelli K, Temiz-Arpaci O, Yalcin I, Aki E, Ozkan S and Kaynak F 2009 Synthesis, biological evaluation and 2D-QSAR analysis of benzoxazoles as antimicrobial agents Eur. J. Med. Chem. 44 501

    Article  CAS  Google Scholar 

  6. Ansari K F and Lal C 2009 Synthesis, physicochemical properties and antimicrobial activity of some new benzimidazole derivatives Eur. J. Med. Chem. 44 4028

    Article  CAS  Google Scholar 

  7. Refaat H M 2010 Synthesis and anticancer activity of some novel 2-substituted benzimidazole derivatives Eur. J. Med. Chem. 45 2949

    Article  CAS  Google Scholar 

  8. Zhao J, Sun B, Qiu L, Caocen H, Li Q, Chen X and Yan F 2012 Efficient light-scattering functionalized \(\text{ TiO }_{2}\) photoanodes modified with cyanobiphenyl-based benzimidazole for dye-sensitized solar cells with additive-free electrolytes J. Mater. Chem. 22 18380

    Article  CAS  Google Scholar 

  9. Saluja P, Sharma H, Kaur N, Singh N and Jang D O 2012 Benzimidazole-based imine-linked chemosensor: chromogenic sensor for \(\text{ Mg }_{2}^{+}\) and fluorescent sensor for \(\text{ Cr }_{3}^{+}\) Tetrahedron 68 2289

    Article  CAS  Google Scholar 

  10. Ooyama Y, Egawa H and Yoshida K 2008 A new class of fluorescent dye for sensing water in organic solvents by photo-induced electron transfer – A (Phenylamino)naphtho[1,2-\(d\)]oxazol-2-yl-type fluorophore with both proton-binding and proton-donating sites Eur. J. Org. Chem. 5239

  11. Kawashita Y, Nakamichi N, Kawabata H and Hayashi M 2003 Direct and practical synthesis of 2-arylbenzoxazoles promoted by activated carbon Org. Lett. 5 3713

    Article  CAS  Google Scholar 

  12. Blacker A J, Farah M M, Hall M I, Marsden S P, Saidi O and Williams J M J 2009 Synthesis of benzazoles by hydrogen-transfer catalysis Org. Lett. 11 2039

    Article  CAS  Google Scholar 

  13. Bahrami K, Khodaei M M and Naali F 2009 \(\text{ H }_{2}\text{ O }_{2}/\text{ Fe }(\text{ NO }_{3})_{3}\)-promoted synthesis of 2-arylbenzimidazoles and 2-arylbenzothiazoles Synlett 569

  14. Zhang C, Zhang L and Jiao N 2012 Catalyst free approach to benzimidazoles using air as the oxidant at room temperature Green. Chem. 14 3273

    Article  CAS  Google Scholar 

  15. Chen Y-X, Qian L-F, Zhang W and Han B 2008 Efficient aerobic oxidative synthesis of 2-substituted benzoxazoles, benzothiazoles, and benzimidazoles catalyzed by 4-methoxy-TEMPO Angew. Chem. Int. Edit. 47 9330

    Article  CAS  Google Scholar 

  16. Wen X, El Bakali J, Deprez-Poulain R and Deprez B 2012 Efficient propylphosphonic anhydride (®T3P) mediated synthesis of benzothiazoles, benzoxazoles and benzimidazoles Tetrahedron Lett. 53 2440

    Article  CAS  Google Scholar 

  17. Aridoss G and Laali K K 2011 Building heterocyclic systems with RC(OR)\(_{2}^{+}\) carbocations in recyclable brønsted acidic ionic liquids: Facile synthesis of 1-substituted 1\(H\)-1,2,3,4-tetrazoles, benzazoles and other ring systems with CH(OEt)\(_{3}\) and EtC(OEt)\(_{3}\) in [\(\text{ EtNH }_{3}][\text{ NO }_{3}\)] and \([\text{ PMIM }(\text{ SO }_{3}\text{ H })][\text{ OTf }]\) Eur. J. Org. Chem. 2827

  18. Smellie I A S, Fromm A, Fabbiani F, Oswald I D H, White F J and Paton R M 2010 Synthesis of 2-pyranosyl benzothiazoles, benzimidazoles and benzoxazoles via nucleophilic addition reactions of pyranosyl nitrile oxides Tetrahedron 66 7155

    Article  CAS  Google Scholar 

  19. Kidwai M, Jahan A and Bhatnagar D 2010 Polyethylene glycol: a recyclable solvent system for the synthesis of benzimidazole derivatives using CAN as catalyst J. Chem. Sci. 122 607

    Article  CAS  Google Scholar 

  20. Liu J, Wang C, Ma X, Shi X, Wang X, Li H and Xu Q 2016 Simple synthesis of Benzazoles by substrate promoted CuI-catalyzed aerobic oxidative cyclocondensation of \(o\)-Thio/Amino/Hydroxyanilines and amines under air Catal. Catal. Lett. 146 2139

    Article  CAS  Google Scholar 

  21. Kumar B, Smita K, Kumar B and Cumbal L 2014 Ultrasound promoted and \(\text{ SiO }_{2}/\text{ CCl }_{3}\)COOH mediated synthesis of 2-aryl-1-arylmethyl-1\(H\)-benzimidazole derivatives in aqueous media: An eco-friendly approach J. Chem. Sci. 126 1831

    Article  CAS  Google Scholar 

  22. Bala M, Verma P K, Sharma D, Kumar N and Singh B 2015 Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles Mol. Divers. 19 263

    Article  CAS  Google Scholar 

  23. Vahdat S M, Raz S G and Baghery S 2014 Application of nano \(\text{ SnO }_{2}\) as a green and recyclable catalyst for the synthesis of 2-aryl or alkylbenzoxazole derivatives under ambient temperature J. Chem. Sci. 126 579

    Article  CAS  Google Scholar 

  24. Praveen C, Nandakumar A, Dheenkumar P, Muralidharan D and Permal P T 2012 Microwave-assisted one-pot synthesis of benzothiazole and benzoxazole libraries as analgesic agents J. Chem. Sci. 124 609

    Article  CAS  Google Scholar 

  25. Sharma P and Gupta M 2016 1,3,5-Trimethylpyrazolium chloride based ionogel as an efficient and reusable heterogeneous catalyst for the synthesis of benzimidazoles J. Chem. Sci. 128 61

    Article  CAS  Google Scholar 

  26. Peng J, Ye M, Zong C, Hu F, Feng L, Wang X, Wang Y and Chen C 2011 Copper-catalyzed intramolecular C-N bond formation: A straightforward synthesis of benzimidazole derivatives in water J. Org. Chem. 76 716

    Article  CAS  Google Scholar 

  27. Sadig J E R, Foster R, Wakenhut F and Willis M C 2012 Palladium-catalyzed synthesis of benzimidazoles and quinazolinones from common precursors J. Org. Chem. 77 9473

    Article  CAS  Google Scholar 

  28. Vaillard V A, Guastavino J F, Budén M E, Bardagí J I, Barolo S M and Rossi R A 2012 Synthesis of 6-substituted 2-pyrrolyl and indolyl benzoxazoles by intramolecular \(o\)-arylation in photostimulated reactions J. Org. Chem. 77 1507

    Article  CAS  Google Scholar 

  29. Baars H, Beyer A, Kohlhepp S V and Bolm C 2014 Transition-metal-free synthesis of benzimidazoles mediated by KOH/DMSO Org. Lett. 16 536

    Article  CAS  Google Scholar 

  30. Yang D, Zhu X, Wei W, Jiang M, Zhang N, Ren D, You J and Wang H 2014 Magnetic copper ferrite nanoparticles: An inexpensive, efficient, recyclable catalyst for the synthesis of substituted benzoxazoles via Ullmann-type coupling under ligand-free conditions Synlett 729

  31. Mayo M S, Yu X, Zhou X, Feng X, Yamamoto Y and Bao M 2014 Convenient synthesis of benzothiazoles and benzimidazoles through brønsted acid catalyzed cyclization of 2-amino thiophenols/anilines with \(\beta \)-diketones Org. Lett. 16 764

    Article  CAS  Google Scholar 

  32. Mayo M S, Yu X, Zhou X, Feng X, Yamamoto Y and Bao M 2014 Synthesis of benzoxazoles from 2-aminophenols and \(\beta \)-diketones using a combined catalyst of brønsted acid and copper iodide J. Org. Chem. 79 6310

    Article  CAS  Google Scholar 

  33. Huang X, Li X, Zou M, Song S, Tang C, Yuan Y and Jiao N 2014 From ketones to esters by a Cu-catalyzed highly selective C(CO)–C(alkyl) bond cleavage: Aerobic oxidation and oxygenation with air J. Am. Chem. Soc. 136 14858

    Article  CAS  Google Scholar 

  34. Zhang C, Feng P and Jiao N 2013 Cu-catalyzed esterification reaction via aerobic oxygenation and C–C bond cleavage: an approach to \(\upalpha \)-ketoesters J. Am. Chem. Soc. 135 15257

  35. Wang R, Wang S Y and Ji S-J 2014 Water promoted C–C bond cleavage: facile synthesis of 3,3-bipyrrole derivatives from dienones and tosylmethyl isocyanide (TosMIC) Org. Biomol. Chem. 12 1735

    Article  CAS  Google Scholar 

  36. Liu H, Dong C, Zhang Z, Wu P and Jiang X 2012 Transition-metal-free aerobic oxidative cleavage of C-C bonds in \(\upalpha \)-hydroxy ketones and mechanistic insight to the reaction pathway Angew. Chem. Int. Edit. 51 12570

    Article  CAS  Google Scholar 

  37. Telvekar V N and Jadhav N C 2008 Simple system for oxidation of alcohols in aqueous solution Synth. Commun. 38 3107

    Article  CAS  Google Scholar 

  38. Telvekar V N, Patel K N, Kundaikar H S and Chaudhari H K 2008 A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate Tetrahedron Lett. 49 2213

    Article  CAS  Google Scholar 

  39. Bachhav H M, Takale B S and Telvekar V N 2013 Efficient synthesis of Bis(4-Dimethaminophenyl)arylmethanes and Bis(4-Diamethaminophenyl) alkanes using iodine reagent Synth. Commun. 43 1909

    Article  CAS  Google Scholar 

  40. Nguyen T B, Ermolenko L, Dean W A and Al-Mourabit A 2012 Benzazoles from aliphatic amines and \(o\)-amino/mercaptan/hydroxyanilines: Elemental sulfur as a highly efficient and traceless oxidizing agent Org. Lett. 14 5948

    Article  CAS  Google Scholar 

  41. Kim J, Kim J, Lee H, Lee B M and Kim B H 2011 Indium-mediated one-pot benzimidazole synthesis from 2-nitroanilines or 1,2-dinitroarenes with orthoesters Tetrahedron 67 8027

    Article  CAS  Google Scholar 

  42. Zhang Z-H, Li J-J, Gao Y-Z and Liu Y-H 2007 Synthesis of 2-substituted benzimidazoles by iodine-mediated condensation of orthoesters with 1,2-phenylenediamines J. Heterocyclic Chem. 44 1509

    Article  CAS  Google Scholar 

  43. Kim Y, Kumar M R, Park N, Heo Y and Lee S 2011 Copper-catalyzed, one-pot, three-component synthesis of benzimidazoles by condensation and C–N bond formation J. Org. Chem. 76 9577

    Article  CAS  Google Scholar 

  44. Huang X and Tang J 2003 Solid phase synthesis of benzothiazole and thiophene derivatives based on resin-bound cyclic malonic acid ester Tetrahedron 59 4851

    Article  CAS  Google Scholar 

  45. Li K-L Du Z-B, Guo C-C and Chen Q-Y 2009 Regioselective syntheses of 2- and 4-formylpyrido[2,1–\(b\)]benzoxazoles J. Org. Chem. 74 3286

  46. Mohammadpoor-Baltork I, Khosropour A R and Hojati S F 2007 \(\text{ ZrOCl }_{2}{\cdot }8\text{ H }_{2}\text{ O }\) as an efficient, environmentally friendly and reusable catalyst for synthesis of benzoxazoles, benzothiazoles, benzimidazoles and oxazolo\([4,5-b]\)pyridines under solvent-free conditions Catal. Commun. 8 1865

    Article  CAS  Google Scholar 

Download references

Acknowledgements

S.B.B. and S.M.G are thankful to the University Grants Commission (UGC, New Delhi, India), and V.N.T. is thankful to the Sciences and Engineering Research Board (SERB), New Delhi, India for providing financial support.

Author information

Authors and Affiliations

  1. Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Matunga, Mumbai, Maharashtra, 400 019, India

    Saket B Bhagat, Shrikant M Ghodse & Vikas N Telvekar

Authors
  1. Saket B Bhagat
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shrikant M Ghodse
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vikas N Telvekar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vikas N Telvekar.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (pdf 567 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bhagat, S.B., Ghodse, S.M. & Telvekar, V.N. Sodium dichloroiodate promoted C-C bond cleavage: An efficient synthesis of 1,3-Benzazoles via condensation of \({\varvec{o}}\)-amino/mercaptan/hydroxyanilines with \({\varvec{\beta }}\)-diketones. J Chem Sci 130, 10 (2018). https://doi.org/10.1007/s12039-017-1414-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-017-1414-z

Keywords

Search

Navigation