Skip to main content
SpringerLink
Log in

Cobalt-promoted regioselective preparation of aryl tetrazole amines

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

Abstract

A highly general, efficient and simple methodology for the regioselective synthesis of aryl tetrazole amines has been explored. The present method involves consecutive desulphurization and \(C\hbox {-}N\) cross-coupling reaction. Cheap, readily available and air stable cobalt catalyst has been used for this methodology. In addition, the substrate scope has been demonstrated.

Graphical Abstract

A highly general, efficient and simple methodology for the regioselective synthesis of aryl tetrazole amines has been explored. The present method involves consecutive desulphurization and \(C\hbox {-}N\) cross-coupling reaction.

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

Fig. 1
Scheme 1
Scheme 2
Scheme 3

Similar content being viewed by others

References

  1. (a) Ford R E, Knowles P, Lunt E, Marshall S M, Penrose A J, Ramsden C A, Summers A J H, Walker J L and Wright D E 1986 Synthesis and quantitative structure-activity relationships of antiallergic 2-hydroxy-N-(1\(H\)-tetrazol-5-yl)benzamides and \(N\)-(2-hydroxyphenyl)-1\(H\)-tetrazole-5-carboxamides J. Med. Chem. 29 538; (b) Peet N P, Baugh L E, Sundler S, Lewis J E, Matthews E H, Olberding E L and Shah D N 1986 3-(1\(H\)-Tetrazol-5-yl)-4(3\(H)\)-quinazolinone sodium salt (MDL 427): a new antiallergic agent J. Med. Chem. 29 2403

  2. Girijavallabhan V M, Pinto P A, Genguly A K and Versace R W 1988 Eur. Patent, EP274867 1989 Aromatic Hydroxyketones: Preparation & Physical Properties Chem. Abstr. 110 23890

  3. (a) Akimoto H, Ootsuand K and Itoh F 1993 Eur. Patent EP530537, Green synthesis of the 1-substituted 1\(H\)-1,2,3,4-tetrazoles by application of the Natrolite zeolite as a new and reusable heterogeneous catalyst Chem. Abstr. 119 226417; (b) Taveras A G, Mallams A K and Afonso A 1998 Int. patent WO9811093 Tricyclic inhibitors of farnesyl protein transferase Chem. Abstr. 128 230253

  4. (a) Wittenberger S 1994 Recent developments in tetrazole chemistry, a review Org. Prep. Proced. Int. 26 499; (b) Herr R J and Biorg 2002 5-Substituted-1\(H\)-tetrazoles as carboxylic acid isosteres: medicinal chemistry and synthetic methods Med. Chem. 10 3379; (c) Wistrandand LG and Frejd T 2003 Synthesis of fused tetrazole- and imidazole derivatives via iodocyclization Tetrahedron 59 6759; (d) Flippin L A 1991 Directed metalation and new synthetic transformations of 5-aryltetrazoles Tetrahedron Lett. 32 6857; (e) Rhonnstad P and Wensbo D 2002 On the relative strength of the 1\(H\)-tetrazol-5-yl- and the 2-(triphenylmethyl)-2\(H\)-tetrazol-5-yl-group in directed ortho-lithiation Tetrahedron Lett. 43 3137

  5. (a) Jen K A, Holm A and Rachlin S 1966 Acta Chem. Scand. 20 2795; (b) Percival D and Herbst R M 1957 Alkylated 5-Aminotetrazoles, Their Preparation and Properties J. Org. Chem. 22 925; (c) Finnegan W G, Henry R A and Lieber E 1953 Preparation and isomerization of 5-alkylaminotetrazoles J. Org. Chem. 18 779

  6. (a) Moderhack D, Goos K H and Preu L 1990 Organic Reaction Mechanisms, An annual survey covering the literature Chem. Ber. 123 1575; (b) Gbrecht W L and Herbst R M 1953 The synthesis of certain 5-aminotetrazole derivatives II. The action of hydrazoic acid on monoalkylcyanamides J. Org. Chem. 18 1014; (c) Herbst R, Roberts C W and Harvill E 1951 The synthesis of 5-aminotetrazole derivatives J. Org. Chem. 16 139; (d) Marchalin M, Martvon A and Collect C 1980 Reactions of pyridyl isothiocyanates with diazoalkanes and azoimide Collect. Czech. Chem. Commun. 45 2329

  7. (a) Klich M and Teutsch G 1986 Synthese de N-(tetrazol-5-yl) azetidin-2-ones Tetrahedron 42 2677; (b) Barlin G B 1967 The relative electron-releasing power of a singly bound, and the electron-attracting power of a doubly bound nitrogen atom when present in the same five-membered ring J. Chem. Soc. B 641

  8. Ried W, Erle H and Liebigs E 1982 Science of Synthesis: Houben-Weyl Methods of Molecular Transformation Ann. Chem. 201

  9. (a) Batey R A and Powell D A 2000 A General Synthetic Method for the Formation of Substituted 5-Aminotetrazoles from Thioureas: A Strategy for Diversity Amplification Org. Lett. 2 3237; (b) Yu Y, Ostresh J M and Houghten R A 2004 Solid-phase synthesis of 5-aminotetrazole Tetrahedron Lett. 45 7787

  10. Ramesh Y, Nilufa K, Saroj Kumar R and Bhisma K P 2011 Tandem regioselective synthesis of tetrazoles and related heterocycles using iodine Org. Biomol. Chem. 9 3235

  11. (a) Demko Z P and Sharpless K B 2001 Preparation of 5-Substituted 1\(H\)-Tetrazoles from Nitriles in Water J. Org. Chem. 66 7945; (b) Demko Z P and Sharpless K B 2002 An Expedient Route to the Tetrazole Analogues \(\upalpha \) -Amino Acids Org. Lett. 4 2525; (c) Himo F, Demko Z P, Noodleman L and Sharpless K B 2002 Mechanisms of Tetrazole Formation by Addition of Azide to Nitriles J. Am. Chem. Soc. 124 12210; (d) Himo F, Demko Z P, Noodleman L and Sharpless K B 2003 Why Is Tetrazole Formation by Addition of Azide to Organic Nitriles Catalyzed by Zinc(II) Salts? J. Am. Chem. Soc. 125 9983

  12. (a) Lakshmikantam M, Shiva Kumar K B and Sridhar C 2005 Nanocrystalline ZnO as an Efficient Heterogeneous Catalyst for the Synthesis of 5-Substituted 1\(H\)-Tetrazoles Adv. Synt. Catal. 347 1212; (b) Lakshmikantam M, Balasubrahmanyam V and Shiva Kumar K B 2006 Zinc Hydroxyapatite–Catalyzed Efficient Synthesis of 5-Substituted 1\(H\)-Tetrazoles Synth. Commun. 36 1809; (c) Lakshmi Kantam M, Shiva Kumar K B and Phani Raja K 2006 An efficient synthesis of 5-substituted 1\(H\)-tetrazoles using Zn/Al hydrotalcite catalyst J. Mol. Catal. A: Chem. 247 186

  13. Amantini D, Beleggia R, Fringuelli F, Pizzo F and Vaccoro L 2004 TBAF-Catalyzed Synthesis of 5-Substituted 1\(H\)-Tetrazoles under Solventless Conditions J. Org. Chem. 69 2896

  14. Tienan J, Fukuzou K, Shin K and Yoshinori Y 2008 Copper-catalyzed synthesis of 5-substituted 1\(H\)-tetrazoles via the [3+2] cycloaddition of nitriles and trimethylsilyl azide Tetrahedron Lett. 49 2824

  15. Nasrollahzadeh M, Habibi D, Shahkarami Z and Bayat Y 2009 A general synthetic method for the formation of arylaminotetrazoles using natural natrolite zeolite as a new and reusable heterogeneous catalyst Tetrahedron 65 10715

  16. (a) Ramana T and Punniyamurthy T 2012 preparation of 2-Azido-1-Substituted-1 \(H\)-Benzo[\(d\)]imidazoles Using a Copper-Promoted Three-Component Reaction and Their Further Conversion into 2-Amino and 2-Triazolyl Derivatives Chem. Eur. J. 18 13279; (b) Pinapati S, Mandapati U and Rudraraju R R 2017 Iron-Mediated Desulphurization Towards the Synthesis of 2-Halo Aromatic Isothio cyanates Chemistry Select. 2 295; (c) Usharani M, Srinivasarao P and Rameshraju R 2017 Copper promoted desulfurization towards the synthesis of isothiocyanates Tetrahedron Lett. 58 125; (d) Mohan S, Bajavali S and Prasadrao K 2016 Cobalt Mediated by Desulphurization Towards the Synthesis of Isothiocyanates Synth. Comm. 46 1759

  17. (a) Batey R A and Powell D A 2000 A General Synthetic Method for the Formation of Substituted 5-Aminotetrazoles from Thioureas: A Strategy for Diversity Amplification Org. Lett. 2 3237; (b) Mohan S, Bajavali S, Ramana T and Prasadrao K 2016 An efficient methodology for the synthesis of thioureas from amine mediated by a cobalt source Tetrahedron Lett. 57 5297; (c) Mohan S, Bajavali S and Prasadrao K 2016 Cobalt Mediated by Desulphurization Towards the Synthesis of Isothiocyanates Synth. Comm. 46 1759; (d) Ali A R, Ghosh H and Patel B K 2010 A greener synthetic protocol for the preparation of carbodiimide Tetrahedron Lett. 51 1019; (e) Guin S, Rout S K, Gogoi A, Nandi S, Ghara K K and Patel B K 2012 Desulfurization Strategy in the Construction of Azoles Possessing Additional Nitrogen, Oxygen or Sulfur using a Copper(I) Catalyst Adv. Synth. Catal. 354 2757

  18. (a) Zhao D, Hu J, Wu N, Huang X, Qin X and Lan J You 2011 Regiospecific Synthesis of 1,2-Disubstituted (Hetero)aryl Fused Imidazoles with Tunable Fluorescent Emission Org. Lett. 13 6516; (b) Deng X, Mc Allister H and Mani N S 2009 CuI-Catalyzed Amination of Arylhalides with Guanidines or Amidines: A Facile Synthesis of 1-\(H\)-2-Substituted Benzimidazoles J. Org. Chem. 74 5742; (c) Lv X and Bao W 2009 Copper-Catalyzed Cascade Addition/Cyclization: An Efficient and Versatile Synthesis of \(N\)-Substituted 2-Heterobenzimidazoles J. Org. Chem. 74 5618; (d) Saha P, Ali M A, Ghosh P and Punniyamurthy T 2010 Cobalt-catalyzed intramolecular \(C\)–\(N\) and \(C\)–\(O\) cross-coupling reactions: synthesis of benzimidazoles and benzoxazoles Org. Biomol. Chem. 8 5692; (e) Cahiez G and Moyeux A 2010 Cobalt-Catalyzed Cross-Coupling Reactions Chem. Rev. 110 1435; (f) Tan B Y H and Teo Y O 2014 Efficient cobalt-catalyzed \(C\)–\(N\) cross-coupling reaction between benzamide and aryl iodide in water Org. Biomol. Chem. 12 7478; (g) Amatore M and Gosmini C 2008 Synthesis of functionalized diarylmethanes via a cobalt-catalyzed cross-coupling of arylzinc species with benzyl chlorides Chem. Commun. 5019; (h) Li B, Wu Z H, Gu Y F, Sun C L, Wang B Q and Shi Z J 2011 Domino Condensation/S-Arylation/Heterocyclization Reactions: Copper-Catalyzed Three-Component Synthesis of 2-\(N\)-Substituted Benzothiazoles Angew. Chem. Int. Edit. 123 1141; (i) Hammann J M, Haas D and Knochel P 2015 Cobalt-catalyzed negishi cross-coupling reactions of (hetero) arylzinc reagents with primary and secondary alkyl bromides and iodides Angew. Chem. Int. Edit. 54 447; (j) Zhao D, Hu J, Wu N, Huang X, Qin X, Lan J and You 2011 Regiospecific Synthesis of 1,2-Disubstituted (Hetero)aryl Fused Imidazoles with Tunable Fluorescent Emission J. Org. Lett. 13 6516; (k) Deng X, Mc Allister H and Mani N S J 2009 CuI-Catalyzed Amination of Arylhalides with Guanidines or Amidines: A Facile Synthesis of 1-\(H\)-2-Substituted Benzimidazoles J. Org. Chem. 74 5742; (l) Lv X and Bao W J 2009 Copper-Catalyzed Cascade Addition/Cyclization: An Efficient and Versatile Synthesis of \(N\)-Substituted 2-Heterobenzimidazoles J. Org. Chem. 74 5618

  19. (a) Larsso P F, Correa A, Carril M, Norrby P O and Bolm C 2009 Copper-catalyzed cross-couplings with part-per-million catalyst loadings Angew. Chem. Int. Edit. 48 5691; (b) Buchwald S L and Bolm C 2009 On the Role of Metal Contaminants in Catalyses with \(\text{FeCl}_{3}\) Angew. Chem. Int. Edit. 48 5586

Download references

Acknowledgements

Authors thank Gitam University, Hyderabad for providing the laboratory facility for the experimental work. Authors also thank Dr. Ramana for truthful discussions during our experimental work.

Author information

Authors and Affiliations

  1. Jawaharlal Nehru Technological University Kakinada, Kakinada, Andhra Pradesh, 533 003, India

    Kondraganti Lakshmi

  2. Department of Chemistry, Gitam School of Technology, Gitam University, HTP Campus, Rudraram, Medak, Telangana, 502 329, India

    Manabolu Surendra Babu

  3. Department of Chemistry, Acharya Nagarjuna University, Guntur, Andhra Pradesh, 522 510, India

    Dittakavi Ramachandran

Authors
  1. Kondraganti Lakshmi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Manabolu Surendra Babu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Dittakavi Ramachandran
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Manabolu Surendra Babu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (pdf 3496 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lakshmi, K., Babu, M.S. & Ramachandran, D. Cobalt-promoted regioselective preparation of aryl tetrazole amines. J Chem Sci 130, 46 (2018). https://doi.org/10.1007/s12039-018-1453-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-018-1453-0

Keywords

Search

Navigation