Synthesis of 1,2,4-Benzotriazines via Copper(I) Iodide/1H-Pyrrole-2-carboxylic Acid Catalyzed Coupling of o-Haloacetanilides and N-Boc Hydrazine

Yijun Zhou; Zhigao Zhang; Yongwen Jiang; Xianhua Pan; Dawei Ma

doi:10.1055/s-0034-1378708

Synlett, Table of Contents

Synlett 2015; 26(11): 1586-1590
DOI: 10.1055/s-0034-1378708

letter

Synthesis of 1,2,4-Benzotriazines via Copper(I) Iodide/1H-Pyrrole-2-carboxylic Acid Catalyzed Coupling of o-Haloacetanilides and N-Boc Hydrazine

Authors

Yijun Zhou

^aSchool of Perfume and Aroma Technology, Shanghai Institute of Technology, No. 120 Cao Bao Road, Shanghai 200235, P. R. of China
Zhigao Zhang

^bState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Email: madw@mail.sioc.ac.cn
Yongwen Jiang

^bState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Email: madw@mail.sioc.ac.cn
Xianhua Pan*

^aSchool of Perfume and Aroma Technology, Shanghai Institute of Technology, No. 120 Cao Bao Road, Shanghai 200235, P. R. of China
Dawei Ma*

^bState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China Email: madw@mail.sioc.ac.cn

Abstract

All articles of this category

Abstract

Coupling of o-haloacetanilides and N-Boc hydrazine proceeded at room temperature under the catalysis of CuI/1H-pyrrole-2-carboxylic acid. The coupling products underwent oxidation to afford the azo compounds, which were subjected to deprotection with TFA and in situ cyclization to give 1,2,4-benzotriazines.

Key words

coupling - cyclization - copper - catalysis - 1,2,4-benzotriazine

Full Text

References

References and Notes
1 Hay MP, Hicks KO, Pchalek K, Lee HH, Blaser A, Pruijn FB, Anderson RF, Shinde SS, Wilson WR, Denny WA. J. Med. Chem. 2008; 51: 6853
2 Noronha G, Barrett K, Cao J, Dneprovskaia E, Fine R, Gong X, Gritzen C, Hood J, Kang X, Klebansky B, Li G, Lose D, Mark C, McPherson A, Palanki M, Pathak V, Renick J, Soll R, Splittgerber U, Wrasidlo W, Zeng B, Zhao N, Zhou Y. Bioorg. Med. Chem. Lett. 2006; 16: 5546
3 Boyle RG, Travers S. WO 2008015429, 2008
4 Zeller M. WO 9838161, 1998
5 Lee J, Lee S, Seo H, Kim M, Kang S, Kim J, Lee S, Jung M, Son E, Lee J, Song K, Kim M. WO 2010147430, 2010
6 Settimo FD, Primofiore G, Taliani S, Marini AM, La Motta C, Simorini F, Salerno S, Sergianni V, Tuccinardi T, Martinelli A, Cosimelli B, Greco G, Novellino E, Ciampi O, Trincavelli ML, Martini C. J. Med. Chem. 2007; 50: 5676
7 Fleck F, Balzer H, Aebli H. FR 1411433, 1965
8 Selby T. US 5389600, 1995
9 Leverenz K, Schuendehuette K. DE 2241259, 1974

10a Riccardo C, Alessandro B, Fabio S. J. Heterocycl. Chem. 1979; 16: 1005
10b Reich M, Fabio P, Lee V, Kuck N, Testa R. J. Med. Chem. 1989; 32: 2474

11 Bass JY, Caravella JA, Chen L, Creech KL, Deaton DN, Madauss KP, Marr HB, McFadyen RB, Miller AB, Mills WY, Navas FIII, Parks DJ, Smalley TL. Jr, Spearing PK, Todd D, Williams SP, Wisely GB. Bioorg. Med. Chem. Lett. 2011; 21: 1206
12 Guo H, Liu J, Wang X, Huang G. Synlett 2012; 23: 903

13a Chen Y, Ma D. Org. Lett. 2006; 8: 6115
13b Chen Y, Xie X, Ma D. J. Org. Chem. 2007; 72: 9329
13c Lu B, Wang B, Zhang Y, Ma D. J. Org. Chem. 2007; 72: 5337
13d Zou B, Yuan Q, Ma D. Angew. Chem. Int. Ed. 2007; 46: 2598
13e Ma D, Xie S, Xue P, Zhang X, Dong J, Jiang Y. Angew. Chem. Int. Ed. 2009; 48: 4222
13f Ma D, Geng Q, Zhang H, Jiang Y. Angew. Chem. Int. Ed. 2010; 49: 1291
13g Shi L, Liu X, Zhang H, Jiang Y, Ma D. J. Org. Chem. 2011; 76: 4200
13h Ma D, Lu X, Shi L, Zhang H, Jiang Y, Liu X. Angew. Chem. Int. Ed. 2011; 50: 1118
13i Xu L, Jiang Y, Ma D. Org. Lett. 2012; 14: 1150

14 For copper-catalyzed oxidation of aryl hydrazines to azo compounds, see: Zhang C, Jiao N. Angew. Chem. Int. Ed. 2010; 49: 6174

15a Jiang L, Lu X, Zhang H, Jiang Y, Ma D. J. Org. Chem. 2009; 74: 4542
15b Xiong X, Jiang Y, Ma D. Org. Lett. 2012; 14: 2552

16a Wolter M, Klapars A, Buchwald SL. Org. Lett. 2001; 3: 3803
16b Lam MS, Lee HW, Chan AC, Kwong FY. Tetrahedron Lett. 2008; 49: 6192

17 General Procedure for the Preparation of 9 A Schlenk tube was charged with iodide 7 (0.5 mmol), N-Boc hydrazine (70 mg, 0.53 mmol), CuI (5 mg, 0.025 mmol), 1H-pyrrole-2-carboxylic acid (9 mg, 0.08 mmol), NaI (15 mg, 0.1 mmol), and K₂CO₃ (138 mg, 1.0 mmol), evacuated, and backfilled with argon. DMSO (1.5 mL) was successively added. The reaction mixture was stirred at 25 °C for 24–30 h before oxygen was introduced. After the reaction mixture was stirred at 25 °C for 3–5 h, it was extracted with EtOAc. The combined organic phase was washed with brine and dried over Na₂SO₄. After concentration in vacuo, the residue was purified by column chromatography on silica gel to provide 9. Compound 9a: ¹H NMR (500 MHz, CDCl₃): δ = 9.54 (s, 1 H), 8.70 (dd, J = 8.5, 1.1 Hz, 1 H), 7.74 (dd, J = 8.2, 1.5 Hz, 1 H), 7.54 (ddd, J = 8.6, 7.5, 1.5 Hz, 1 H), 7.09 (ddd, J = 8.4, 7.3, 1.3 Hz, 2 H), 2.41 (t, J = 7.4 Hz, 2 H) 1.80–1.72 (m, 2 H), 1.65 (s, 9 H), 1.00 (t, J = 7.4 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 171.66, 160.23, 138.25, 138.05, 136.01, 123.11, 120.55, 119.36, 84.97, 40.16, 27.85 (3C), 18.75, 13.68. ESI-MS: m/z = 314.2 [M + Na]⁺. ESI-HRMS:m/z calcd for C₁₅H₂₂N₃O₃ ⁺ [M + H]⁺: 292.1656; found: 292.1653. Compound 9k: ¹H NMR (500 MHz, CDCl₃): δ = 11.10 (s, 1 H), 8.83 (dd, J = 8.5, 1.1 Hz, 1 H), 7.95 (dd, J = 8.1, 1.6 Hz, 1 H), 7.71 (dd, J = 3.8, 1.1 Hz, 1 H), 7.62 (dd, J = 7.3, 1.4 Hz, 1 H), 7.59 (dd, J = 5.0, 1.0 Hz, 1 H), 7.22 (ddd, J = 8.3, 7.4, 1.2 Hz, 1 H), 7.14 (dd, J = 5.0, 3.8 Hz, 1 H), 1.71 (s, 9 H). ¹³C NMR (125 MHz, CDCl₃): δ = 160.30, 159.14, 139.74, 138.01, 136.45, 136.30, 131.71, 128.83, 127.88, 125.30, 123.50, 120.31, 84.95, 27.88 (3 C). ESI-MS: m/z = 354.2 [M + Na]⁺. ESI-HRMS:m/z calcd for C₁₆H₁₈N₃O₃S⁺ [M + H]⁺: 332.1063; found: 332.1061.
18 Typical Procedure for the Prepration of 10 To a solution of 9 (0.2 mmol) in CH₂Cl₂ (2.0 mL) was added TFA (0.5 mL). The solution was stirred at r.t. for 2 h before aq NaHCO₃ (5 mL) was added. The mixture was extracted with CH₂Cl₂. The organic phase was dried over Na₂SO₄, filtered, and concentrated under vacuum. The residue was purified by column chromatography on silica gel to provide 10. Compound 10a: ¹H NMR (400 MHz, CDCl₃): δ = 8.49 (d, J = 8.4 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 1 H), 7.96–7.90 (m, 1 H), 7.83–7.77 (m, 1 H), 3.35 (t, J = 9.6 Hz, 2 H), 2.08–1.97 (m, 2 H), 1.06 (t, J = 7.4 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.45, 146.18, 140.85, 135.25, 129.82, 129.53, 128.51, 39.69, 22.28, 13.92. ESI-MS: m/z = 174.1 [M + H]⁺. ESI-HRMS:m/z calcd for C₁₀H₁₂N₃ ⁺ [M + H]⁺: 174.1026; found: 174.1025. Compound 10h: ¹H NMR (500 MHz, CDCl₃): δ = 8.46 (dd, J = 8.4, 0.7 Hz, 1 H), 8.35 (dd, J = 3.7, 1.1 Hz, 1 H), 8.02–7.97 (m, 1 H), 7.92 (ddd, J = 8.4, 6.8, 1.3 Hz, 1 H), 7.76 (ddd, J = 8.2, 6.8, 1.3 Hz, 1 H), 7.61 (dd, J = 5.0, 1.1 Hz, 1 H), 7.24 (dd, J = 4.9, 3.7 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 157.36, 146.00, 140.87, 140.72, 135.72, 131.31, 130.61, 129.75, 129.70, 128.65, 128.61. ESI-MS: m/z = 214.1 [M + H]⁺. ESI-HRMS:m/z calcd for C₁₁H₈N₃S⁺ [M + H]⁺: 214.0433; found: 214.0432.

Supplementary Material

Supporting Information (PDF)