Compound 8

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InChIKey WVVOPDUZHUYLIH-UHFFFAOYSA-N

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

A suspension of 5-bromoisophthalic acid (0.245 g, 1.00 mmol) in thionyl chloride (10 mL) was stirred at reflux under dry nitrogen for 2 h. Evaporation of excess thionyl chloride under reduced pressure gave an off-white solid. This residue was dissolved in dichloromethane (50 mL), and 1-pyrenemethylamine hydrochloride (0.536 g, 2.00 mmol) and triethylamine (1 mL) were added to the solution. The mixture was stirred at room temperature overnight, and the resulting solid was filtered off, washed with water (3×30 mL) and methanol (2×40 mL), and dried to yield a cream crystalline solid (0.659 g, 95%). M.p. 310 °C; ¹H NMR (250 MHz, DMSO-d₆) δ (ppm)=9.49 (t, J=5.4 Hz, 2H), 8.51 (s, 1H), 8.48 (d, J=9.3 Hz, 2H), 8.31 – 8.23 (m, 10 H), 8.15 (s, 4H), 8.12 – 8.04 (m, 4H), 5.23 (d, J=5.4 Hz, 4H); ¹³C NMR (62.5 MHz, DMSO-d₆) δ (ppm)=164.2, 136.5, 132.4, 130.7, 130.3, 130.2, 128.1, 127.6, 127.4, 127.1, 126.9, 126.2, 125.9, 125.3, 125.2, 124.7, 124.0, 123.9, 123.2, 122.9, 121.7, 41.2; IR (Nujol): 1649, 1637 (νC=O), 1376 (νC-N), 846 cm⁻¹; MS (MALDI-TOF): m/z=693. Calcd. for [C₄₂H₂₇BrN₂O₂+Na]⁺ 693. Analysis (calcd., found for C₄₂H₂₇BrN₂O₂): C (75.11, 75.01), H (4.05, 4.02), N (4.17, 4.15%).

To a suspension of this bromo-substituted intermediate (0.336 g, 0.500 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.029 g, 0.025 mmol) in toluene (500 mL) was added ferroceneboronic acid (0.120 g, 0.520 mmol) and sodium carbonate (0.106 g, 1.00 mmol) in water (5 mL). The mixture was heated under reflux for 2 days, cooled and diluted with toluene (200 mL) and water (200 mL). The organic phase was washed with 5% HCl, then with water, dried over MgSO₄, and evaporated to dryness. The crude product was purified by column chromatography (dichloromethane as eluent) to give 8 as a yellow, crystalline solid (0.284 g, 73% yield), m.p. 243 °C; ¹H NMR (250 MHz, DMSO-d₆) δ (ppm)=9.41 (t, J=5.4 Hz, 2H), 8.54 (d, J=9.3 Hz, 2H), 8.33 – 8.25 (m, 9H), 8.21 (d, J=1.5 Hz, 2H), 8.16 (s, 4H), 8.15 – 8.04 (m, 4H), 5.28 (d, J=5.4 Hz, 4H), 4.88 (s, 2H), 4.38 (s, 2H), 4.01 (s, 5H); ¹³C NMR (62.5 MHz, DMSO-d₆) δ (ppm)=166.2, 140.3, 135.0, 133.2, 131.1, 130.7, 130.5, 128.5, 128.0, 127.8, 127.4, 127.3, 127.1, 126.6, 125.6, 125.5, 125.1, 124.6, 124.4, 124.3, 123.6, 83.7, 69.8, 69.7, 67.0; 43.5; IR (Nujol): 1620 (νC=O), 1376 (νC-N), 845 cm⁻¹; MS (MALDI-TOF): m/z=777. Calcd. for [C₅₂H₃₆FeN₂O₂+H]⁺, 777; for [C₅₂H₃₆FeN₂O₂+Na]⁺, calcd. 799; found 799; Analysis (calcd., found for C₅₂H₃₆FeN₂O₂): C (80.41, 79.95), H (4.67, 4.66), N (3.61, 3.59%).