Copper-catalyzed N-Arylation of Aryl Iodides with Benzamides or Nitrogen Heterocycles in the Presence of Ethylenediamine

Abstract

The copper-catalyzed N-arylation of benzamides or nitrogen heterocycles was carried out with catalytic CuI (10 mol%) in the presence of ethylenediamine (10 mol%) as a ligand and K₃PO₄ or Cs₂CO₃ as a base under mild conditions.

Key words

copper-catalyst - N-arylation - benzamides - nitrogen heterocycles

References

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7

Selected physical and spectral data are as follows. 3b: mp 88 °C (hexane-ethyl acetate). ¹H NMR (500 MHz, CDCl₃, δ ppm) 6.90 (1 H, dd, J = 5.5 and 1.5 Hz), 6.85 (1 H, dd, J = 5.5 and 3.7 Hz), 6.45 (1 H, dd, J = 3.7 and 1.5 Hz), 4.50 (2 H, m), 4.00 (2 H, m). ¹³C NMR (125 MHz, CDCl₃, δ ppm) 154.62, 140.33, 124.65, 118.13, 110.93, 62.21, 46.03. IR (KBr, cm^-1): 1726, 1545, 1483, 1035. HRMS: calcd for C₇H₇NO₂S: 169.0197, found: 169.0194. 3d: mp 196 °C (hexane-ethyl acetate). ¹H NMR (500 MHz, CDCl₃, δ ppm) 8.15 (1 H, m), 7.88 (1 H, m), 7.78 (2 H, m), 7.06 (1 H, dd, J = 5.5 and 1.5 Hz), 6.91 (1 H, dd, J = 5.5 and 3.7 Hz), 6.78 (1 H, dd, J = 3.7 and 1.5 Hz). ¹³C NMR (125 MHz, CDCl₃, δ ppm) 162.83, 147.69, 140.22, 134.88, 132.29, 131.95, 130.30, 125.08, 118.60, 113.18. IR (KBr, cm^-1): 3235, 3118, 2888, 1636, 1574, 1527, 1354. HRMS: calcd for C₁₁H₈N₂O₃S: 248.0256, found: 248.0254. 3h: mp 162 °C (hexane-ethyl acetate). ¹H NMR (500 MHz, CDCl₃, δ ppm) 8.13 (1 H, d, J = 8.8 Hz), 7.74 (1 H, m), 7.64 (2 H, m), 7.38 (1 H, s), 7.23 (1 H, s), 6.84 (1 H, s), 2.33 (6 H, s). ¹³C NMR (125 MHz, DMSO-d₆, δ ppm) 164.85, 147.36, 139.67, 138.68, 134.92, 133.69, 131.74, 130.12, 126.32, 125.09, 118.29, 21.96. IR (KBr, cm^-1): 3256, 1657, 1523, 1350, 836. HRMS: calcd for C₁₅H₁₄N₂O₃: 270.1004, found: 270.1007. 3i: mp 80 °C (pentane-ether). ¹H NMR (500 MHz, CDCl₃, δ ppm) 9.95 (1 H, s), 8.61 (1 H, m), 8.23 (1 H, m), 7.91 (1 H, m), 7.48 (1 H, m), 7.44 (2 H, s) 6.80 (1 H, s) 2.34 (6 H, s). ¹³C NMR (125 MHz, CDCl₃, δ ppm) 162.31, 150.40, 148,36, 139.21, 138.08, 138.00, 126.77, 126.52, 122.78, 117.87, 21.85. IR (KBr, cm^-1): 3341, 2913, 1683, 1540, 1458. HRMS: calcd for C₁₄H₁₄N₂O: 226.1106, found: 226.1117. 3m: mp 154 °C (methylene chloride). ¹H NMR (500 MHz, CDCl₃, δ ppm) 10.53 (1 H, s), 8.13 (2 H, d, J = 8.1 Hz), 7.86 (2 H, m), 7.75 (2 H, m), 7.57 (2 H, d, J = 8.8 Hz), 6.94 (2 H, d, J = 8.8 Hz) 3.74 (3 H, s). ¹³C NMR (125 MHz, CDCl₃, δ ppm) 164.49, 156.61, 147.48, 134.84, 133.65, 132.83, 131.72, 130.14, 125.09, 122.11, 114.82, 56.08. IR (KBr,
cm^-1): 3263, 1650, 1532, 1350, 1251. HRMS: calcd for C₁₄H₁₂N₂O₄: 272.0797, found: 272.0793. 3n: mp 192 °C (hexane-ethyl acetate). ¹H NMR (500 MHz, DMSO-d₆, δ ppm) 10.46 (1 H, s), 8.37 (2 H, d, J = 9.2 Hz), 8.17 (2 H, d, J = 9.2 Hz), 7.68 (2 H, d, J = 9.2 Hz), 6.95 (2 H, d, J = 9.2 Hz), 3.75 (3 H, s). ¹³C NMR (125 MHz, DMSO-d₆, δ ppm) 164.23, 156.75, 149.91, 141.57, 132.61, 129.95, 124.38, 122.94, 114.69, 56.05. IR (KBr, cm^-1): 3295, 2951, 1648, 1527, 1342. HRMS: calcd for C₁₄H₁₂N₂O₄: 272.0797, found: 272.0793. 3o: mp 90 °C (hexane-ethyl acetate). ¹H NMR (500 MHz, DMSO-d₆, δ ppm) 10.54 (1 H, s), 8.73 (1 H, m), 8.14 (1 H, m), 8.01 (1 H, m), 7.81 (2 H, d, J = 8.8 Hz), 7.66 (1 H, m) 6.93 (2 H, d, J = 8.8 Hz), 3.75 (1 H, m). ¹³C NMR (125 MHz, DMSO-d₆, δ ppm) 163.09, 156.65, 150.64, 149.32, 138.98, 132.05, 127.68, 123.06, 122.76, 114.72, 56.05. IR (KBr,
cm^-1): 3263, 1650, 1532, 1350, 1251. HRMS: calcd for C₁₃H₁₂N₂O₂: 228.0899, found: 228.0897.