60% |
With barium dihydroxide;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 6h; |
A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.2 g, 0.76 mmol), 3- cyanophenylboronic acid (0.223 g, 1.52 mmol), barium hydroxide (0.285 g, 1.67 mmol), Pd(PPh3)4 (0.088 g, 0.076 mmol), DME (5 mL) and H2O (3 mL) was heated (800C) for 6 hours with vigorous stirring under an argon atmosphere. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a plug of celite. The filtrate was diluted with brine; the organic phase was separated, dried (MgSO4) and concentrated in vacuo. The residue obtained was purified by flash column chromatography (20percent diethyl.bul. ether-hexane) to give 75 (0.130 g, 60percent yield) as a viscous liquid. 1H NMR (500 MHz, CDCl3) delta 7.85 (t, J = 2.5 Hz, IH), 7.78 (dt, J = 7.5 Hz, J = 1.5 Hz, IH), 7.63 (dt, J = 8.0 Hz, J = 1.5 Hz, IH), 7.53 (t, J = 8.0 Hz, IH), 7.46 (d, J = 7.5 Hz, 2H)5 7.44- 7.37 (m, 3H)5 7.35 (t, J = 7.0 Hz, IH), 7.18-7.14 (m, 2H), 7.02 (dd, J = 8.5 Hz5 J = 2.5 Hz, IH)5 5.17 (s, 2H). |
60% |
With barium dihydroxide; water;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 80℃; for 6h; |
A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.2 g, 0.76 mmol), 3- cyanophenylboronic acid (0.223 g, 1.52 mmol), barium hydroxide (0.285 g, 1.67 mmol), Pd(PPh3)4 (0.088 g, 0.076 mmol), DME (5 mL) and H2O (3 niL) was heated (80°C) for 6 hours with vigorous stirring under an argon atmosphere. The reaction mixture was cooled to RT, diluted with ethyl acetate, and filtered through a plug of celite. The filtrate was diluted with brine; the organic phase was separated, dried (MgSO4), and concentrated in vacuo. The residue obtained was purified by flash column chromatography (20percent diethyl ether-hexane) to give 75 (0.130 g, 60percent yield) as a viscous liquid.[0411] 75 was confirmed as follows: 1H NMR (500 MHz, CDCl3) delta 7.85 (t, J = 2.5 Hz, 1H), 7.78 (dt, J = 7.5 Hz, J = 1.5 Hz, 1H), 7.63 (dt, J = 8.0 Hz, J = 1.5 Hz, 1H), 7.53 (t, J = 8.0 Hz, 1H), 7.46 (d, J = 7.5 Hz, 2H), 7.44-7.37 (m, 3H), 7.35 (t, J = 7.0 Hz, 1H), 7.18-7.14 (m, 2H), 7.02 (dd, J = 8.5 Hz, J = 2.5 Hz, 1H), 5.17 (s, 2H). |
60% |
With barium dihydroxide;Pd(PPh3)4; In 1,2-dimethoxyethane; water; |
3-(3-Benzyloxy-phenyl)benzonitrile (51) A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.2 g, 0.76 mmol), 3-cyanophenylboronic acid (0.223 g, 1.52 mmol), barium hydroxide (0.285 g, 1.67 mmol), Pd(PPh3)4 (0.088 g, 0.076 mmol), DME (5 mL) and H2O (3 mL) was heated (80° C.) for 6 hours with vigorous stirring under an argon atmosphere. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a plug of celite. The filtrate was diluted with brine; the organic phase was separated, dried (MgSO4) and concentrated in vacuo. The residue obtained was purified by flash column chromatography (20percent diethyl ether-hexane) to give 51 (0.130 g, 60percent yield) as a viscous liquid. 1H NMR (500 MHz, CDCl3) delta 7.85 (t, J=2.5 Hz, 1H), 7.78 (dt, J=7.5 Hz, J=1.5 Hz, 1H), 7.63 (dt, J=8.0 Hz, J=1.5 Hz, 1H), 7.53 (t, J=8.0 Hz, 1H), 7.46 (d, J=7.5 Hz, 2H), 7.44-7.37 (m, 3H), 7.35 (t, J=7.0 Hz, 1H), 7.18-7.14 (m, 2H), 7.02 (dd, J=8.5 Hz, J=2.5 Hz, 1H), 5.17 (s, 2H). |