Copper-Mediated Sequential C–N and N–N Bond Formation: Facile Synthesis of Symmetrical 1,2,4-Triazoles

Zhonglian Li; Zhiguo Zhang; Wei Zhang; Qingfeng Liu; Tongxin Liu; Guisheng Zhang

doi:10.1055/s-0033-1338985

Synlett, Table of Contents

Synlett 2013; 24(20): 2735-2739
DOI: 10.1055/s-0033-1338985

letter

Copper-Mediated Sequential C–N and N–N Bond Formation: Facile Synthesis of Symmetrical 1,2,4-Triazoles

Zhonglian Li

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

,

Zhiguo Zhang*

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

,

Wei Zhang

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

,

Qingfeng Liu

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

,

Tongxin Liu

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

,

Guisheng Zhang*

Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China Fax: +86(373)3325250 Email: zhangzg@htu.edu.cn Email: zgs6668@yahoo.com

› Author Affiliations

Abstract

All articles of this category

Abstract

Via a one-pot process, catalyzed by Cu(OAc)₂, a series of 3,5-disubstituted 4H-1,2,4-triazoles was conveniently and efficiently synthesized by using low-toxicity, stable, readily available, inexpensive amidine hydrochloride.

Key words

1,2,4-triazoles - copper - amidine hydrochloride - N–N bond coupling - de-amine reaction

Full Text

References

References and Notes
1 Hull JW, Romer DR, Adaway TJ, Podhorez DE. Org. Process Res. Dev. 2009; 13: 1125
2 Sun J, Zhang A, Zhang J, Xie X, Liu W. J. Agric. Food. Chem. 2011; 60: 160
3 Haddadin MJ, Ghazvini Zadeh EH. Tetrahedron Lett. 2010; 51: 1654
4 Khanmohammadi H, Erfantalab M. Spectrochim. Acta, Part A 2012; 86: 39
5 Zhang J.-P, Zheng S.-L, Huang X.-C, Chen X.-M. Angew. Chem. Int. Ed. 2004; 43: 206
6 Zhang J.-P, Zhang Y.-B, Lin J.-B, Chen X.-M. Chem. Rev. 2011; 112: 1001

7a Ueda S, Nagasawa H. J. Am. Chem. Soc. 2009; 131: 15080
7b Yeung K.-S, Farkas ME, Kadow JF, Meanwell NA. Tetrahedron Lett. 2005; 46: 3429

8a Buscemi S, Vivona N, Caronna T. J. Org. Chem. 1996; 61: 8397
8b Holzer M, Dobner B, Briel D. Liebigs Ann. Chem. 1994; 895

9a Huntsman E, Balsells J. Eur. J. Org. Chem. 2005; 3761
9b Reichelt A, Falsey JR, Rzasa RM, Thiel OR, Achmatowicz MM, Larsen RD, Zhang D. Org. Lett. 2010; 12: 792

10a Yin P, Ma W.-B, Chen Y, Huang W.-C, Deng Y, He L. Org. Lett. 2009; 11: 5482
10b Wang L.-Y, Tseng W.-C, Lin H.-Y, Wong FF. Synlett 2011; 1467

11 Zhang J.-P, Lin Y.-Y, Huang X.-C, Chen X.-M. J. Am. Chem. Soc. 2005; 127: 5495
12 Xu H, Jiang Y, Fu H. Synlett 2013; 24: 125

13a Poulsen TB, Jørgensen KA. Chem. Rev. 2008; 108: 2903
13b Ma D, Cai Q. Acc. Chem. Res. 2008; 41: 1450
13c Zhang C, Tang C, Jiao N. Chem. Soc. Rev. 2012; 41: 3464

14a Daugulis O, Do H.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
14b Díez-González S, Nolan SP. Acc. Chem. Res. 2008; 41: 349
14c Kumar MR, Park A, Park N, Lee S. Org. Lett. 2011; 13: 3542

15a Zhang Q, Zhang Z, Yan Z, Liu Q, Wang T. Org. Lett. 2007; 9: 3651
15b Zhang Z, Zhang Q, Sun S, Xiong T, Liu Q. Angew. Chem. Int. Ed. 2007; 46: 1726
15c Zhang Z, Zhang Q, Yan Z, Liu Q. J. Org. Chem. 2007; 72: 9808
15d Zhang Z, Zhang Q, Ni Z, Liu Q. Chem. Commun. 2010; 46: 1269
15e Zhang Z, Xue C, Liu X, Zhang Q, Liu Q. Tetrahedron 2011; 67: 7081
15f Zhang Z, Fang S, Liu Q, Zhang G. Adv. Synth. Catal. 2012; 354: 927
15g Bi J, Zhang Z, Liu Q, Zhang G. Green Chem. 2012; 14: 1159

16 See the Supporting Information for more information.

17a Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879
17b Wu X.-F, Neumann H, Beller M. Chem. Rev. 2012; 113: 1

18a Schaefer FC, Hechenbleikner I, Peters GA, Wystrach VP. J. Am. Chem. Soc. 1959; 81: 1466
18b Rosenberg MG, Brinker UH. J. Org. Chem. 2003; 68: 4819
18c Oxley P, Short WF. J. Chem. Soc. 1949; 449

19 Ashley JN, Barber HJ, Ewins AJ, Newbery G, Self AD. H. J. Chem. Soc. 1942; 103

20a Bates CG, Saejueng P, Doherty MQ, Venkataraman D. Org. Lett. 2004; 6: 5005
20b Tye JW, Weng Z, Johns AM, Incarvito CD, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 9971
20c Xu Z, Thompson LK, Miller DO. Inorg. Chem. 1997; 36: 3985
20d Op’t Holt BT, Vance MA, Mirica LM, Heppner DE, Stack TD. P, Solomon EI. J. Am. Chem. Soc. 2009; 131: 6421

21 Yang D, Fu H, Hu L, Jiang Y, Zhao Y. J. Org. Chem. 2008; 73: 7841

22a Neumann JJ, Suri M, Glorius F. Angew. Chem. Int. Ed. 2010; 49: 7790
22b Suri M, Jousseaume T, Neumann JJ, Glorius F. Green Chem. 2012; 14: 2193

23 General Procedure for the Synthesis of Compounds 2a–o: To a round-bottom flask (25 mL) equipped with a spherical condenser (40 cm length) were added amidine hydrochloride 1 (1.0 mmol), Cu(OAc)₂ (0.2 equiv), K₂CO₃ (2.0 equiv), 1,10-phenanthroline (0.1 equiv) and anhyd DMF (2.0 mL). Then the mixture was well stirred at 130 °C under an inert atmosphere. After cooling off, the mixture was filtered through a pad of celite eluting with CH₂Cl₂ (3 × 6 mL). The volatiles were removed under reduced pressure and the residue was purified by a short flash silica gel column chromatography to give compound 2. 2a: white solid; eluent: petroleum ether–EtOAc (3:1). Yield: 86%; mp 191–192 °C. ¹H NMR (400 MHz, CD₃OD): δ = 8.05 (d, J = 6.4 Hz, 4 H), 7.41–7.49 (m, 6 H). ¹³C NMR (100 MHz, CD₃OD): δ = 160.53, 131.02, 130.17, 129.89, 127.56. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₁N₃: 222.1026; found: 222.1026. General Procedure for the Synthesis of Compounds 2p: To a round-bottom flask (25 mL) equipped with a spherical condenser (40 cm length) were added acetimidamide hydrochloride 1p (94.5 mg, 1.0 mmol), benzimidamide hydrochloride 1a (0.5 equiv), Cu(OAc)₂ (37 mg, 0.2 mmol), K₂CO₃ (276 mg, 2.0 mmol), 1,10-phenanthroline (20 mg, 0.1 mmol) and anhyd DMF (2.0 mL). Then the mixture was well stirred at 130 °C under an inert atmosphere. The other two batches of benzimidamide hydrochloride 1a (0.5 equiv for each) were added to the mixture every 8.0 h. After 48 h (total reaction time), the reaction mixture was cooled, filtered through a pad of celite eluting with CH₂Cl₂ (3 × 6 mL). The volatiles were removed under reduced pressure and the residue was purified by short flash silica gel column chromatography to give compound 2p as a white solid; eluent: petroleum ether–EtOAc (2:1). Yield: 68%; mp 161–163 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.03 (d, J = 6.0 Hz, 2 H), 7.44 (d, J = 6.0 Hz, 3 H), 2.53 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 161.04, 155.71, 130.08, 129.73, 128.89, 126.44, 12.81. HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₉N₃: 160.0869; found: 160.0874. General Procedure for the Synthesis of Compounds 3a,b: To a round-bottom flask (25 mL) equipped with a spherical condenser (40 cm length) were added amidine hydrochloride 1s or 1t (1.0 mmol), Cu(OAc)₂ (0.2 equiv), K₂CO₃ (2.0 equiv), 1,10-phenanthroline (0.1 equiv) and anhyd DMF (2.0 mL). Then the mixture was well stirred at 130 °C under an inert atmosphere. After cooling off, the mixture was filtered through a pad of celite eluting with CH₂Cl₂ (3 × 6 mL). The volatiles were removed under reduced pressure and the residue was purified by a short flash silica gel column chromatography to give compound 3a or 3b. 3a: yellow solid; yield: 80%; mp 81–83 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.35 (d, J = 8.8 Hz, 2 H), 6.62 (d, J = 8.4 Hz, 2 H), 4.28 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 150.80, 133.67, 120.41, 114.33, 99.30. 3b: white solid; yield: 86%; mp 110–113 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.55 (d, J = 8.8 Hz, 2 H), 6.95 (d, J = 8.8 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 160.57, 134.47, 119.42, 116.63, 102.80.
24 Toth B. In Vivo 2000; 14: 299

Supplementary Material

Supporting Information