Binap, (A+-)- → 2-(2,2,3,3-Tetrafluoro-2,3-dihydrobenzo[b][1,4]dioxin-6-ylamino)-6-(3-acetamidophenyl)pyrazine

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Reaction Steps

Following Method L, 2-(3-acetamidophenyl)-6-chloropyrazine (4a) (60 mg, 0.24 mmol), 2,2,3,3-tetrafluoro-6-amino-1,4-benzodioxene (78.1 mg, 0.35 mmol), Pd(0)2 dba3 (9 mg, 0.01 mmol), BINAP (50 mg, 0.04 mmol), sodium tert-butoxide (33 mg, 0.34 mmol) and toluene (5 mL) were reacted at 85° C. for 16 hours. Evaporation under vacuo followed. The resulting solid was washed with 50 mL dichloromethane and filtered. The insoluble solid was dissolved in 3 mL of hot ethyl acetate. When this mixture was allowed to cool down in the freezer some crystals appeared. Filtration and washing with 2 mL of cold ethyl acetate gave 10.8 mg of the title compound. Yield: 10.4%. 1 H NMR (250 MHz, DMSO-d6) δ 2.08 (s, 3 H), 7.44 (d, 1 H, J=9.1 Hz), 7.47 (d, 1 H, J=7.8 Hz), 7.59 (bd, 1 H, J=7.6 Hz), 7.704-7.759 (m, 2 H), 7.96 (d, 1 H, 2.4 Hz), 8.21 (s, 1 H), 8.45 (bs, 1 H), 8.51 (s, 1 H), 9.95 (s, 1 H), 10.10 (s, 1 H); 13C NMR (62.9 MHZ, DMSO-d6) δ 24.00, 106.13, 115.92, 117.34, 118.01, 120.13, 121.08, 129.31, 130.04, 130.98, 133.62, 136.16, 136.79, 139.03, 139.99, 147.90, 150.84, 168.40; m/z 435.1 [(M+H)+, calcd for C20H14F4N4O3 434.1].

Provenance & Evidence