Citation: Satish Gaddam, Harshavardhan Reddy Kasireddy, Karnakar Konkala, Ramesh Katla, Nageswar Yadavalli Venkata Durga. Synthesis of N-substituted-2-aminobenzothiazoles using nano copper oxide as a recyclable catalyst under ligand-free conditions, in reusable PEG-400 medium[J]. Chinese Chemical Letters, ;2014, 25(05): 732-736. doi: 10.1016/j.cclet.2014.02.003 shu

Synthesis of N-substituted-2-aminobenzothiazoles using nano copper oxide as a recyclable catalyst under ligand-free conditions, in reusable PEG-400 medium

1.
CSIR-Medicinal Chemistry and Pharmacology Division, Indian Institute of Chemical Technology, Hyderabad 500007, India

Corresponding author: Nageswar Yadavalli Venkata Durga,
Received Date: 11 July 2013
Available Online: 21 February 2014

A simple and practical method for the synthesis of N-substituted-2-aminobenzothiazoles via a crosscoupling reaction of 2-iodo anilines with isothiocyanates is envisaged using nano copper oxide as a recyclable catalyst and Cs₂CO₃ as a base in PEG-400, as a bio-degradable, reusable, inexpensive and nontoxic reaction medium, under ligand-free conditions. The present tandem process underlines environmental acceptability to access a wide range of N-substituted-2-aminobenzothiazoles in good to excellent yields.
- 2-Aminobenzothiazoles,
- 2-Iodoanilines,
- Isothiocyanates,
- CuO nanoparticles,
- Recyclability,
- PEG-400
1. [1]
  [1] A.C. Gyorkos, C.P. Corrette, S.Y. Cho, et al., Efficient conversion of substituted aryl thioureas to 2-aminobenzothiazoles using benzyltrimethylammonium tribromide, WO Patent 44 (2005) 793.
2. [2]
  [2] A.D. Jordan, C. Luo, A.B. Reitz, A new three-carbon synthon for efficient synthesis of benzannelated and 1-(2-arylethenyl) heterocycles, J. Org. Chem. 68 (2003) 8693-8696.
3. [3]
  [3] A.R. Katritzky, D.O. Tymoshenko, D. Monteux, et al., Efficient conversion of substituted aryl thioureas to 2-aminobenzothiazoles using benzyltrimethylammonium tribromide, J. Org. Chem. 65 (2000) 8059-8062.
4. [4]
  [4] A.R. Katritzky, D.O. Tymoshenko, D. Monteux, et al., A new three-carbon synthon for efficient synthesis of benzannelated and 1-(2-arylethenyl) heterocycles, J. Org. Chem. 65 (2000) 8059-8062.
5. [5]
  [5] I.ĆAleta, M. Kralj, M. Marjanovic, et al., Novel cyano- and amidinobenzothiazole derivatives: synthesis, antitumor evaluation, and X-ray and quantitative structure-activity relationship (QSAR) analysis, J. Med. Chem. 52 (2009) 1744-1756.
6. [6]
  [6] H. Suter, H. Zutter, Studien iiber benzthiazole als eventuelle orale antidiabetica, Helv. Chim. Acta 50 (1967) 1084-1086.
7. [7]
  [7] V.G. Shirke, A.S. Bobade, R.P. Bhamaria, B.G. Khadse, S.R. Sengupta, Synthesis and antitubercular activity of some new 2-(substituted arylamino)-5,6-disubstituted/ 6-substituted benzothiazoles, Drugs (India) 27 (1990) 350-353.
8. [8]
  [8] S.J. Hays, M.J. Rice, D.F. Ortwine, et al., Substituted 2-benzothiazolamines as sodium flux inhibitors: quantitative structure-activity relationships and anticonvulsant activity, J. Pharm. Sci. 83 (1994) 1425-1432.
9. [9]
  [9] W. Aelterman, Y. Lang, B. Willemsens, et al., Conversion of the laboratory synthetic route of the N-aryl-2-benzothiazolamine R116010 to a manufacturing method, Org. Process Res. Dev. 5 (2001) 467-471.
10. [10]
  [10] Z. Li, S.X. Xiao, G.Q. Tian, et al., Microwave promoted environmentally benign synthesis of 2-aminobenzothiazoles and their urea derivatives, Phosphorus Sulfur Silicon 183 (2008) 1124-1126.
11. [11]
  [11] T. Suzuki, S. Igari, A. Hirasawa, Identification of G protein-coupled receptor 120- selective agonists derived from PPARγ agonists, J. Med. Chem. 51 (2008) 7640- 7644.
12. [12]
  [12] H.F. Motiwala, R. Kumar, A.K. Chakraborti, Microwave-accelerated solvent- and catalyst-free synthesis of 4-aminoaryl/alkyl-7-chloroquinolines and 2-aminoaryl/ alkylbenzothiazoles, Aust. J. Chem. 60 (2007) 369-374.
13. [13]
  [13] F. Delmas, A. Avellaneda, C. Di Giorgio, et al., Synthesis and antileishmanial activity of (1,3-benzothiazol-2-yl) amino-9-(10H)-acridinone derivatives, Eur. J. Med. Chem. 39 (2004) 685-690.
14. [14]
  [14] J. Das, R.V. Moquin, J. Lin, et al., Discovery of 2-amino-heteroaryl-benzothiazole- 6-anilides as potent p56lck inhibitors, Bio. Med. Chem. Lett. 13 (2003) 2587- 2590.
15. [15]
  [15] J.M. Sprague, A.H. Land, in: R.C. Elderfield (Ed.), The Chemistry of Heterocyclic Compounds, vol. 5, Wiley, New York, 1957, p. 484.
16. [16]
  [16] D. Fajkusova, P. Pazdera, Unexpected formation of benzothiazoles in the synthesis of new heterocycles: benzo-1,2,4-dithiazines, Synthesis 8 (2008) 1297-1305.
17. [17]
  [17] L.L. Joyce, G. Evinda, R.A. Batey, Copper- and palladium-catalyzed intramolecular C-S bond formation: a convenient synthesis of 2-aminobenzothiazoles, Chem. Commun. (2004) 446-447.
18. [18]
  [18] J.W. Qiu, X.G. Zhang, R.Y. Tang, P. Zhong, J.H. Lia, Iron-catalyzed tandem reactions of 2-halobenzenamines with isothiocyanates leading to 2-aminobenzothiazoles, Adv. Synth. Catal. 351 (2009) 2319-2323.
19. [19]
  [19] W. Zhag, Y. Yue, D. Yu, et al., 1,10-Phenanthroline-catalyzed tandem reaction of 2- iodoanilines with isothiocyanates in water, Adv. Synth. Catal. 354 (2012) 2283- 2287.
20. [20]
  [20] D. Ma, X. Lu, L. Shi, et al., Domino condensation/S-arylation/heterocyclization reactions: copper-catalyzed three-component synthesis of 2-N-substituted benzothiazoles, Angew. Chem. Int. Ed. 50 (2011) 1118-1128.
21. [21]
  [21] R. Xiao, W. Hao, J. Ai, M.Z. Cai, A practical synthesis of 2-aminobenzothiazoles via the tandem reactions of 2-haloanilines with isothiocyanates catalyzed by immobilization of copper in MCM-41, J. Organomet. Chem. 705 (2012) 44-50.
22. [22]
  [22] J. Yang, P. Li, L. Wang, Merrifield resin supported phenanthroline Cu(I): a highly efficient and recyclable catalyst for the synthesis of 2-aminobenzothiazoles via the reaction of 2-haloanilines with isothiocyanates, Tetrahedron 67 (2011) 5543- 5549.
23. [23]
  [23] K. Swapna, S.N. Murthy, Y.V.D. Nageswar, Copper iodide as a recyclable catalyst for buchwald N-arylation, Eur. J. Org. Chem. (2010) 6678-6682.
24. [24]
  [24] K. Swapna, S.N. Murthy, Y.V.D. Nageswar, Recyclable heterogeneous copper oxide on alumina catalyzed coupling of phenols and alcohols with aryl halides under ligand-free conditions, Org. Biomol. Chem. 9 (2011) 5978- 5988.
25. [25]
  [25] S.N. Murthy, Y.V.D. Nageswar, O-iodoxybenzoic acid (IBX): a versatile reagent for the synthesis of N-substituted pyrroles mediated by b-cyclodextrin in water, Tetrahedron Lett. 52 (2011) 4481-4484.
26. [26]
  [26] K.H.V. Reddy, V.P. Reddy, J. Shankar, et al., Copper oxide nanoparticles catalyzed synthesis of aryl sulfides via cascade reaction of aryl halides with thiourea, Tetrahedron Lett. 52 (2011) 2679-2682.
27. [27]
  [27] K. Harsha Vardhan Reddy, G. Satish, V. Prakash Reddy, B.S.P. Anil Kumar, Y.V.D. Nageswar, Recyclable Ru/C catalyzed oxidative cyanation of tertiary amines with TBHP, RSC Adv. 2 (2012) 11084-11088.
28. [28]
  [28] K.H.V. Reddy, V.P. Reddy, A.A. Kumar, G. Kranthi, Y.V.D. Nageswar, Nano copper oxide catalyzed synthesis of symmetrical diaryl sulfides under ligand free conditions, Beilstein J. Org. Chem. 7 (2011) 886-891.
29. [29]
  [29] K. Swapna, S.N. Murthy, Y.V.D. Nageswar, Nano-CuFe₂O₄ as a magnetically separable and reusable catalyst for the synthesis of diaryl/aryl alkyl sulfides via cross-coupling process under ligand-free conditions, Org. Biomol. Chem. 9 (2011) 5989-5996.
30. [30]
  [30] K. Ramesh, S.N. Murthy, K. Karnakar, et al., A novel bioglycerol-based recyclable carbon catalyst for an efficient one-pot synthesis of highly substituted imidazoles, Tetrahedron Lett. 53 (2012) 1126-1129.
31. [31]
  [31] K. Ramesh, S.N. Murthy, Y.V.D. Nageswar, Synthesis of N-substituted pyrroles under catalyst- and solvent-free conditions, Synth. Commun. 42 (2012) 2471- 2477.
32. [32]
  [32] K.H.V. Reddy, G. Satish, K. Ramesh, K. Karnakar, Y.V.D. Nageswar, An efficient synthesis of N-substituted indoles from indoline/indoline carboxylic acid via aromatization followed by C-N cross-coupling reaction by using nano copper oxide as a recyclable catalyst, Tetrahedron Lett. 53 (2012) 3061-3065.
33. [33]
  [33] K.H.V. Reddy, G. Satish, K. Ramesh, K. Karnakar, Y.V.D. Nageswar, Magnetically separable CuFe₂O₄ nanoparticle catalyzed C-Se cross coupling in reusable PEG medium, Chem. Lett. 41 (2012) 585-587.
34. [34]
  [34] G. Satish, K.H.V. Reddy, K. Ramesh, K. Karnakar, Y.V.D. Nageswar, Synthesis of 2- N-substituted benzothiazoles via domino condensation-hetero cyclization process, mediated by copper oxide nanoparticles under ligand-free conditions, Tetrahedron Lett. 53 (2012), 2521-2521.
35. [35]
  [35] D. Srimani, A. Bej, A. Sarkar, Palladium nanoparticle catalyzed Hiyama coupling reaction of benzyl halides, J. Org. Chem. 75 (2010) 4296-4299.
36. [36]
  [36] V.V. Namboodiri, R.S. Varma, Microwave-accelerated Suzuki cross-coupling reaction in polyethylene glycol (PEG), Green Chem. 3 (2001) 146- 149.
37. [37]
  [37] Z. Hou, N. Thetssen, W. Leitner, Palladium nanoparticles stabilised on PEGmodified silica as catalysts for the aerobic alcohol oxidation in supercritical carbon dioxide, Green Chem. 9 (2007) 127-132.
38. [38]
  [38] P.C. Andrews, A.C. Peatt, C.L. Raston, Indium metal mediated synthesis of homoallylic amines in poly(propylene)glycol (PPG), Green Chem. 6 (2004) 119-124.
39. [39]
  [39] K.H. Lam, L. Xu, L. Feng, et al., Highly enantioselective iridium-catalyzed hydrogenation of quinoline derivatives using chiral phosphinite H8-BINAPO, Adv. Synth. Catal. 347 (2005) 1755-1759.
40. [40]
  [40] W.B. Wang, S.M. Lu, P.Y. Yang, X.W. Han, Y.G. Zhou, Highly enantioselective iridium-catalyzed hydrogenation of heteroaromatic compounds, quinolines, J. Am. Chem. Soc. 125 (2003) 10536-10540.
41. [41]
  [41] G. Shen, X. Lv, W. Bao, Synthesis of N-substituted-2-aminobenzothiazoles by ligand-free copper(I)-catalyzed cross-coupling reaction of 2-haloanilines with isothiocyanates, Eur. J. Org. Chem. (2009) 5897-5901.
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