Synlett 2015; 26(11): 1586-1590
DOI: 10.1055/s-0034-1378708
letter
© Georg Thieme Verlag Stuttgart · New York

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
a  School of Perfume and Aroma Technology, Shanghai Institute of Technology, No. 120 Cao Bao Road, Shanghai 200235, P. R. of China
,
Zhigao Zhang
b  State 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
b  State 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*
a  School of Perfume and Aroma Technology, Shanghai Institute of Technology, No. 120 Cao Bao Road, Shanghai 200235, P. R. of China
,
Dawei Ma*
b  State 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
› Author Affiliations
Further Information

Publication History

Received: 06 March 2015

Accepted after revision: 07 May 2015

Publication Date:
08 June 2015 (eFirst)

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.

Supporting Information

 
  • References and Notes

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  • 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.