N-Substituted Formamides as C1-Sources for the Synthesis of Benzimidazole and Benzothiazole Derivatives by Using Zinc Catalysts

Deepak B. Nale; Bhalchandra M. Bhanage

doi:10.1055/s-0035-1560319

Synlett, Table of Contents

Synlett 2015; 26(20): 2835-2842
DOI: 10.1055/s-0035-1560319

letter

N-Substituted Formamides as C₁-Sources for the Synthesis of Benzimidazole and Benzothiazole Derivatives by Using Zinc Catalysts

Deepak B. Nale

Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400 019, India Email: bm.bhanage@gmail.com Email: bm.bhanage@ictmumbai.edu.in

,

Bhalchandra M. Bhanage*

Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400 019, India Email: bm.bhanage@gmail.com Email: bm.bhanage@ictmumbai.edu.in

› Author Affiliations

Abstract

All articles of this category

Abstract

An efficient and convenient one-pot protocol has been developed for the synthesis of a variety of benzimidazole, benzoxazole, and benzothiazole derivatives. This novel approach uses various o-phenylenediamines and N-substituted formamides (C₁ sources) in a zinc-catalyzed cyclization in the presence of poly(methylhydrosiloxane) to afford the corresponding derivatives as sole products in moderate to excellent yields.

Key words

formamides - benzenediamines - cyclizations - heterocycles - zinc - catalysis

Full Text

References

References

1a Abonia R, Cortés E, Insuasty B, Quiroga J, Nogueras M, Cobo J. Eur. J. Med. Chem. 2011; 46: 4062
1b Refaat HM. Eur. J. Med. Chem. 2010; 45: 2949
1c Sheng C, Che X, Wang W, Wang S, Cao Y, Yao J, Miao Z, Zhang W. Eur. J. Med. Chem. 2011; 46: 1706
1d Zhang J, Wang J.-L, Zhou Z.-M, Li Z.-H, Xue W.-Z, Xi D, Hao L.-P, Han X.-F, Fei F, Lui T, Liang A.-H. Bioorg. Med. Chem. 2012; 20: 4208
1e Choi SJ, Park HJ, Lee SK, Kim SW, Han G, Choo HY. P. Bioorg. Med. Chem. 2006; 14: 1229
1f Benzimidazoles and Congeneric Tricyclic Compounds . Preston PN. Wiley; New York: 1981. Parts 1 and 2
1g Preston PN. Chem. Rev. 1974; 74: 279

2a Ebenezer WJ, Hutchings MG, Jones K, Lambert DA, Watt I. Tetrahedron Lett. 2007; 48: 1641
2b Yao S, Schafer-Hales KJ, Belfield KD. Org. Lett. 2007; 9: 5645
2c Rodionov VO, Presolski SI, Gardinier S, Lim Y.-H, Finn MG. J. Am. Chem. Soc. 2007; 129: 12696
2d Rudrawar S, Kondaskar A, Chakraborti AK. Synthesis 2005; 2521
2e Chakraborti AK, Rudrawar S, Jadhav KB, Kaur G, Chankeshwara SV. Green Chem. 2007; 9: 1335

3a Alinezhad H, Salehian F, Biparva P. Synth. Commun. 2012; 42: 102
3b Alinezhad H, Salehian F. Synth. React. Inorg. Met.-Org. Chem. 2013; 43: 532
3c Dziewit L, Dmowski M, Baj J, Bartosik D. Appl. Environ. Microbiol. 2010; 76: 1861

4a Seijas JA, Vázquez-Tato MP, Carballido-Reboredo MR, Crecente-Campo J, Romar-López L. Synlett 2007; 313
4b Wen X, El Bakali J, Deprez-Poulain R, Deprez B. Tetrahedron Lett. 2012; 53: 2440
4c Chakraborti AK, Selvam C, Kaur G, Bhagat S. Synlett 2004; 851
4d Phillips MA. J. Chem. Soc. 1928; 172
4e Grimmett MR. Imidazole and Benzimidazole Synthesis . Academic Press; San Diego: 1997

5a Blacker AJ, Farah MM, Marsden SP, Saidi O, Williams JM. J. Tetrahedron Lett. 2009; 50: 6106
5b Su F, Mathew SC, Möhlmann L, Antonietti M, Wang X, Blechert S. Angew. Chem. Int. Ed. 2011; 50: 657
5c Endo Y, Bäckvall J.-E. Chem. Eur. J. 2012; 18: 13609
5d Nguyen TB, Ermolenko L, Dean WA, Al-Mourabit A. Org. Lett. 2012; 14: 5948
5e Yu J, Xu J, Lu M. Appl. Organomet. Chem. 2013; 27: 606
5f Khalafi-Nezhad A, Panahi F. ACS Catal. 2014; 4: 1686
5g Mukhopadhyay C, Ghosh S, Sengupta S, De S. RSC Adv. 2011; 1: 1033

6a Ma D, Xie S, Xue P, Zhang X, Dong J, Jiang Y. Angew. Chem. Int. Ed. 2009; 48: 4222
6b Cheng Y, Yang J, Qu Y, Li P. Org. Lett. 2012; 14: 98

7 Deng H, Li Z, Ke F, Zhou X. Chem. Eur. J. 2012; 18: 4840

8a Vera MD, Pelletier JC. J. Comb. Chem. 2007; 9: 569
8b Evindar G, Batey RA. J. Org. Chem. 2006; 71: 1802
8c Bose DS, Idrees M. J. Org. Chem. 2006; 71: 8261
8d Kashiyama E, Hutchinson I, Chua M.-S, Stinson SF, Phillips LR, Kaur G, Sausville EA, Bradshaw TD, Westwell AD, Stevens MF. G. J. Med. Chem. 1999; 42: 4172
8e Saha P, Ramana T, Purkait N, Ali MA, Paul R, Punniyamurthy T. J. Org. Chem. 2009; 74: 8719

9a Shelkar R, Sarode S, Nagarkar J. Tetrahedron Lett. 2013; 54: 6986
9b Bahrami K, Khodaei MM, Nejati A. Green Chem. 2010; 12: 1237
9c Qiao JX, Wang TC, Hu C, Li J, Wexler RR, Lam PY. S. Org. Lett. 2011; 13: 1804
9d Yu B, Zhang H, Zhao Y, Chen S, Xu J, Huang C, Liu Z. Green Chem. 2013; 15: 95
9e Yu H, Kawanishi H, Koshima H. Heterocycles 2003; 60: 1457
9f Sparke AE, Fisher CM, Mewis RE, Archibald SJ. Tetrahedron Lett. 2010; 51: 4723
9g Mochona M, Le L, Mateeva N, Gangapuram M, Ardley T, Kinfe K. J. Heterocycl. Chem. 2010; 47: 1367
9h Bahrami K, Khodaei MM, Kavianinia I. Synthesis 2007; 547
9i Du L.-H, Wang Y.-G. Synthesis 2007; 675
9j Bahrami K, Khodaei MM, Naali F. J. Org. Chem. 2008; 73: 6835
9k Saha D, Saha A, Ranu BC. Green Chem. 2009; 11: 733
9l Tang L, Guo X, Yang Y, Zha Z, Wang Z. Chem. Commun. 2014; 50: 6145
9m Kattimani PP, Kamble RR, Meti GY. RSC Adv. 2015; 5: 29447
9n Khemnar A, Bhanage BM. RSC Adv. 2014; 4: 8939

10a González J, López LA, Vicente R. Chem. Commun. 2014; 50: 8536
10b Ding G, Lu B, Li Y, Wan J, Zhang Z, Xie X. Adv. Synth. Catal. 2015; 357: 1013
10c Legrave N, Couhert A, Olivero S, Desmurs J.-R, Duñach E. Eur. J. Org. Chem. 2012; 2012: 901
10d Das S, Addis D, Zhou S, Junge K, Beller M. J. Am. Chem. Soc. 2010; 132: 1770
10e González MJ, López LA, Vicente R. Tetrahedron Lett. 2015; 56: 1600

11a Muzart J. Tetrahedron 2009; 65: 8313
11b Ding S, Jiao N. Angew. Chem. 2012; 124: 9360 ; Angew. Chem. Int. Ed. 2012, 51, 9226
11c Kim J, Choi J, Shin K, Chang S. J. Am. Chem. Soc. 2012; 134: 2528
11d Ding S, Jiao N. J. Am. Chem. Soc. 2011; 133: 12374
11e Zhang G, Ren X, Chen J, Hu M, Cheng J. Org. Lett. 2011; 13: 5004
11f Kim J, Chang S. J. Am. Chem. Soc. 2010; 132: 10272
11g Kennedy GL. Jr. Crit. Rev. Toxicol. 1986; 17: 129
11h Sawant DN, Wagh YS, Bhatte KD, Bhanage BM. J. Org. Chem. 2011; 76: 5489

12 Ali W, Rout SK, Guin S, Modi A, Banerjee A, Patel BK. Adv. Synth. Catal. 2015; 357: 515

13a Nale DB, Bhanage BM. Green Chem. 2015; 17: 2480
13b Nale DB, Rana S, Parida KM, Bhanage BM. Catal. Sci. Technol. 2014; 4: 1608
13c Nale DB, Rana S, Parida KM, Bhanage BM. Appl. Catal., A 2014; 469: 340
13d Nale DB, Saigaonkar SD, Bhanage BM. J. CO2 Util. 2014; 8: 67

14 Benzimidazole Derivatives; General Procedure Zn(OAc)₂·2H₂O (5.0 mol%) was transferred to a 100 mL autoclave reactor equipped with an overhead stirrer and an automatic temperature-control system. The appropriate benzene-1,2-diamine 1 (2 mmol), DMF (10.0 mmol), and PMHS (5.0 mmol) were successively introduced. The reactor was sealed, flushed three times with N₂ (10 atm), and heated to the required temperature with vigorous stirring (600 rpm). During the course of the reaction, an increase of pressure was observed, due to the generation of Me₂NH and HCHO at 120 °C.¹⁵ (For this reason, the protocol needs to be performed in a sealed high-pressure reactor.) When the reaction was complete, the autoclave was cooled to r.t., and the pressure generated during the reaction was carefully released. Basic hydrolysis was then carried out at r.t. for 30 min to remove unreacted PMHS from the mixture.^13a The mixture was then extracted with EtOAc (3 × 20 mL). The combined organic layers were dried (Na₂SO₄), filtered, and concentrated in vacuo. The crude products were further purified by column chromatography [silica gel (100–200 mesh), PE–EtOAc (20:4 to 10:2)]. The spectroscopic data for the products were consistent with those reported in the literature.⁹ 6-Methyl-1H-benzimidazole (2b) White solid; yield: 120 mg (91%). ¹H NMR (CDCl₃, 400 MHz, 30 °C, TMS): δ = 8.00 (s, 1 H), 7.55 (d, J = 8 Hz, 1 H), 7.43 (s, 1 H), 7.11 (d, J = 8 Hz, 1 H), 6.16 (s, 1 H), 2.47 (s, 3 H). ¹³C NMR (CDCl₃, 100 MHz, 30 °C, TMS): δ = 140.26, 137.13, 136.03, 132.92, 124.53, 115.44, 114.77, 21.63. GC-MS (EI): m/z (%) = 132 (89) [M + 1]⁺, 131 (100) [M⁺], 104 (20), 77 (25), 66 (10), 51 (17). 1-Methyl-6-nitro-1H-benzimidazole (2g) Yellowish solid; yield: 140 mg (79%). ¹H NMR (CDCl₃, 400 MHz, 30 °C, TMS): δ = 8.39 (s, 1 H), 8.24–8.21 (d, J = 8, 12 Hz, 1 H), 8.12 (s, 1 H), 7.87 (d, J = 12 Hz, 1 H), 3.96 (s, 3 H). ¹³C NMR (CDCl₃, 100 MHz, 30 °C, TMS): δ = 146.75, 142.86, 132.72, 123.35, 119.45, 117.03, 105.45, 28.68. GC-MS (EI): m/z (%) = 178 (12) [M + 1]⁺, 177 (100) [M⁺], 147 (44), 131 (51), 116 (27), 104 (43), 90 (25), 77 (18), 63 (68), 51 (17). 1-Methyl-1H-benzimidazole (2m) Brownish solid; yield: 125 mg (95%). ¹H NMR (CDCl₃, 400 MHz, 30 °C, TMS): δ = 7.82 (s, 1 H), 7.72–7.61 (m, 1 H), 7.34–7.22 (m, 2 H), 3.65 (s, 3 H). ¹³C NMR (CDCl₃, 100 MHz, 30 °C, TMS): δ = 146.37, 143.11, 136.33, 131.87, 126.75, 115.20, 113.44, 29.74. GC-MS (EI): m/z (%) = 133 (9) [M + 1]⁺, 132 (100) [M⁺], 118 (49), 104 (11), 91 (23), 77 (6), 65 (13), 64 (19), 63 (24), 52 (11). N-Methyl-2-nitroaniline (2r) Orange solid; yield: 143 mg (94%). ¹H NMR (CDCl₃, 400 MHz, 30 °C, TMS): δ = 8.11 (d, J = 8 Hz, 1 H), 7.77 (br s, 1 H), 7.46–7.38 (m, 1 H), 6.79 (d, J = 8 Hz, 1 H), 6.61 (m, 1 H), 3.01 (s, 3 H). ¹³C NMR (CDCl₃, 100 MHz, 30 °C, TMS): δ = 146.43, 136.37, 131.96, 126.82, 115.25, 113.46, 29.78. GC-MS (EI) (%): m/z = 154 (9) [M + 2]⁺, 152 (100) [M⁺], 138 (20), 122 (13), 106 (59), 92 (21), 79 (61), 77 (66), 65 (59), 51 (13).
15 Petersen TP, Larsen AF, Ritzén A, Ulven T. J. Org. Chem. 2013; 78: 4190

16a Beyer TA, Scott PJ, Aldinger CE, Dee MF, Siegel TW, Zembrowski WJ, Mylari BL. J. Med. Chem. 1992; 35: 457
16b Song J.-H, Huang C.-S, Nagata K, Yeh JZ, Narahashi T. J. Pharmacol. Exp. Ther. 1997; 282: 707

Supplementary Material

Supporting Information