2,6-dibromo-4-methoxyphenol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ 3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ 3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37–7.42 (m, 2H), 7.45–7.50 (m, 4H), 7.54–7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00. Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ 3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dissolve 2,6-dibromo-4-methoxyphenol (23.0 g, 80.6 mmol) in CH3CN (400 mL) and add trimethylsilyl iodide (TMSI) (53 mL, 371 mmol). Reflux the solution for 4 hours and add more TMSI (50 mL, 371 mmol). Heat the reaction at reflux overnight and cool to ambient temperature. Pour into ice-H2O (700 mL) and extract with EtOAc (2×300 mL). Wash the combined extracts with saturated sodium hydrosulfite (200 mL), H2O (200 mL) and brine (100 mL), dry over MgSO4, filter and concentrate. Crystallize the residue to provide the subtitled product (21.36 g, 98%) as a tan crystalline solid. Reflux the solution for 4 hours Heat the reaction at reflux overnight extract with EtOAc (2×300 mL) Wash the combined extracts with saturated sodium hydrosulfite (200 mL), H2O (200 mL) and brine (100 mL) dry over MgSO4 filter concentrate Crystallize the residue

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 4-methoxyphenol (10.00 g, 80.6 mmol) in CH2Cl2 (70 mL), add a stirred solution of benzyltrimethylammonium tribromide (69.10 g, 177.2 mmol) in CH2Cl2 (500 mL) and MeOH (200 mL). Stir the reaction for 12 hours and remove the solvent in vacuo. Add methyl tert-butyl ether (MTBE) (600 mL) and collect the precipitate (benzyltrimethylammonium bromide) by filtration and wash with MTBE (200 mL). Filter the organics through Celite® and concentrate to provide the subtitled product (23.0 g, >95%) as an orange solid that may be used without purification. 1H NMR (DMSO-d6) δ 3.69 (s, 3H), 7.14 (s, 2H), 9.32 (s, 1H). the reaction for 12 hours remove the solvent in vacuo Add methyl tert-butyl ether (MTBE) (600 mL) and collect the precipitate (benzyltrimethylammonium bromide) by filtration wash with MTBE (200 mL) Filter the organics through Celite® concentrate

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (0.0842 g, 0.691 mmol), Ba(OH)2.8H2O (0.396 g, 1.26 mmol), and Pd(OAc)2 (0.0014 g, 0.00628 mmol) in DME:H2O (6:1, 7 mL) at room temperature was added 2,6-dibromo-4-methoxyphenol (0.0885 g, 0.314 mmol)). The mixture was then heated at 80° C. for 18 h. The reaction was 50% complete, and an additional 2.2 eq. of phenylboronic acid and 0.02 eq. Pd(OAc)2 were added and continued heating for another 24 h. At this point, the reaction was acidified to pH 1 with 1 N HCl and diluted with EtOAc (100 mL). The organic layer was washed with H2O (10 mL) and brine (10 mL) and then dried (MgSO4). After concentration, the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient) to afford the product (0.029 g, 33%) as a clear oil; 1H NMR (CDCl3) δ3.83 (s, 3H), 5.04 (s, 1H), 6.86 (s, 2H), 7.37-7.42 (m, 2H), 7.45-7.50 (m, 4H), 7.54-7.68 (m, 4H); IR (film) 3540, 3060, 2930, 2820, 1605, 1580, 1500, 1470, 1425, 1360, 1330, 1210, 1175, 1120, 1060, 1040, 1025, 755, 700, and 500 cm−1; mass spectrum [EI], m/z 276 (M)+; Anal. Calcd. for C19H16O2.0.80H2O: C, 78.49; H, 6.10; N, 0.00, Found: C, 78.19; H, 5.54; N, 0.19. continued heating for another 24 h The organic layer was washed with H2O (10 mL) and brine (10 mL) dried (MgSO4) After concentration the residue was purified by flash chromatography (1 to 5% EtAOc/petroleum ether gradient)