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Synlett 2015; 26(11): 1586-1590
DOI: 10.1055/s-0034-1378708
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
Weitere Informationen
Publikationsverlauf
Received: 06. März 2015
Accepted after revision: 07. Mai 2015
Publikationsdatum:
08. Juni 2015 (online)
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
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1378708.
- Supporting Information
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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.