3-bromo-4-(dimethylamino)benzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromo-4-(dimethylamino)-benzaldehyde (5 g, 21.92 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl)boronic acid (6.5 g, 26.30 mmol) in a mixture of toluene (50 mL), ethanol (10 mL) and water (7.5 mL) was added potassium carbonate (6.0 g, 43.83 mmol). The solution was degased with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.50 g, 0.438 mmol) was added and the mixture heated at reflux under argon overnight. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (8% ethyl acetate in hexane) to give 7.08 g of 4-dimethylamino-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl)benzaldehyde (92%). 1H NMR (300 MHz; DMSO) 1.22 (s, 3H); 1.28 (s, 3H); 1.29 (s, 3H); 1.31 (s, 3H); 1.69 (s, 4H); 2.07 (s, 3H); 2.64 (s, 6H); 6.93 (d, J=8.4 Hz, 1H); 7.13 (s, 1H); 7.15 (s, 1H); 7.58 (d, J=2.4 Hz, 1H); 7.75 (dd, J1=8.7 Hz, J2=2.1 Hz, 1H); 9.80 (s, 1H). The solution was degased with argon for 30 minutes the mixture heated at reflux under argon overnight washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated The residue was chromatographed on silica gel (8% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-(dimethylamino)-benzaldehyde (10.0 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol). The reaction mixture was stirred at room temperature overnight. The solution was washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. Choromatography on silica gel (15% EtOAc in hexane) afforded 14.06 g of 3-bromo-4-(dimethylamino)-benzaldehyde (92%). The solution was washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-(dimethylamino)-benzaldehyde (10.0 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol). The reaction mixture was stirred at room temperature overnight. The solution was washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. Choromatography on silica gel (15% EtOAc in hexane) afforded 14.06 g of 3-bromo-4-(dimethylamino)-benzaldehyde (92%). The solution was washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromo-4-(dimethylamino)-benzaldehyde (5 g, 21.92 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) boronic acid (6.5 g, 26.30 mmol) in a mixture of toluene (50 mL), ethanol (10 mL) and water (7.5 mL) was added potassium carbonate (6.0 g, 43.83 mmol). The solution was degased with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.50 g, 0.438 mmol) was added and the mixture heated at reflux under argon overnight. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (8% ethyl acetate in hexane) to give 7.08 g of 4-dimethylamino-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehyde (92%). 1H NMR (300 MHz; DMSO) 1.22 (s, 3H); 1.28 (s, 3H); 1.29 (s, 3H); 1.31 (s, 3H); 1.69 (s, 4H); 2.07 (s, 3H); 2.64 (s, 6H); 6.93 (d, J=8.4 Hz, 1H); 7.13 (s, 1H); 7.15 (s, 1H); 7.58 (d, J=2.4 Hz, 1H); 7.75 (dd, J1=8.7 Hz, J2=2.1 Hz, 1H); 9.80 (s, 1H). The solution was degased with argon for 30 minutes the mixture heated at reflux under argon overnight washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated The residue was chromatographed on silica gel (8% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromo-4-(dimethylamino)-benzaldehyde (5 g, 21.92 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) boronic acid (6.5 g, 26.30 mmol) in a mixture of toluene (50 mL), ethanol (10 mL) and water (7.5 mL) was added potassium carbonate (6.0 g, 43.83 mmol). The solution was degased with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.50 g, 0.438 mmol) was added and the mixture heated at reflux under argon overnight. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (8% ethyl acetate in hexane) to give 7.08 g of 4-dimethylamino-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehyde (92%). 1H NMR (300 MHz; DMSO) 1.22 (s, 3H); 1.28 (s, 3H); 1.29 (s, 3H); 1.31 (s, 3H); 1.69 (s, 4H); 2.07 (s, 3H); 2.64 (s, 6H); 6.93 (d, J=8.4 Hz, 1H); 7.13 (s, 1H); 7.15 (s, 1H); 7.58 (d, J=2.4 Hz, 1H); 7.75 (dd, J1=8.7 Hz, J2=2.1 Hz, 1H); 9.80 (s, 1H). The solution was degased with argon for 30 minutes the mixture heated at reflux under argon overnight washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated The residue was chromatographed on silica gel (8% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-(dimethylamino)-benzaldehyde (10.0 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol). The reaction mixture was stirred at room temperature overnight. The solution was washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. Choromatography on silica gel (15% EtOAc in hexane) afforded 14.06 g of 3-bromo-4-(dimethylamino)-benzaldehyde (92%). The solution was washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-dimethylamino-benzaldehyde (10 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol) and the reaction mixture stirred at room temperature overnight. The solution was washed with water and brine, dried (MgSO4), filtered and evaporated. The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane) to give 14.06 g of 3-bromo-4-dimethylamino-benzaldehyde (92%). 1H NMR (300 MHz; CDCl3): δ 2.59 (s, 6 H), 7.06 (d, J=8.1 Hz, 1 H), 7.75 (dd, J=7.8 Hz and 1.5 Hz, 1 H), 5.74 (s, 1 H), 7.06 (d, J=8.1 Hz, 1 H), 7.43 (dd, J=2.1 Hz and 8.4 Hz, 1 H), 8.04 (d, J=1.8 Hz, 1 H), 9.81 (s, 1 H). The solution was washed with water and brine dried (MgSO4) filtered evaporated The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-dimethylamino-benzaldehyde (10 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol) and the reaction mixture stirred at room temperature overnight. The solution was washed with water and brine, dried (MgSO4), filtered and evaporated. The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane) to give 14.06 g of 3-bromo-4-dimethylamino-benzaldehyde (92%). 1H NMR (300 MHz; CDCl3): δ 2.59 (s, 6 H), 7.06 (d, J=8.1 Hz, 1 H), 7.75 (dd, J=7.8 Hz and 1.5 Hz, 1 H), 5.74 (s, 1 H), 7.06 (d, J=8.1 Hz, 1 H), 7.43 (dd, J=2.1 Hz and 8.4 Hz, 1 H), 8.04 (d, J=1.8 Hz, 1 H), 9.81 (s, 1 H). The solution was washed with water and brine dried (MgSO4) filtered evaporated The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-dimethylamino-benzaldehyde (10 g, 67.03 mmol) in dichloromethane (250 mL) was added pyridinium tribromide (21.4 g, 67.03 mmol) and the reaction mixture stirred at room temperature overnight. The solution was washed with water and brine, dried (MgSO4), filtered and evaporated. The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane) to give 14.06 g of 3-bromo-4-dimethylamino-benzaldehyde (92%). 1H NMR (300 MHz; CDCl3): δ 2.59 (s, 6 H), 7.06 (d, J=8.1 Hz, 1 H), 7.75 (dd, J=7.8 Hz and 1.5 Hz, 1 H), 5.74 (s, 1 H), 7.06 (d, J=8.1 Hz, 1 H), 7.43 (dd, J=2.1 Hz and 8.4 Hz, 1 H), 8.04 (d, J=1.8 Hz, 1 H), 9.81 (s, 1 H). The solution was washed with water and brine dried (MgSO4) filtered evaporated The residue was purified on silica gel (eluent: 15% ethyl acetate in hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromo-4-(dimethylamino)-benzaldehyde (5 g, 21.92 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) boronic acid (6.5 g, 26.30 mmol) in a mixture of toluene (50 mL), ethanol (10 mL) and water (7.5.mL) was added potassium carbonate (6.0 g, 43.83 mmol). The solution was degased with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.50 g, 0.438 mmol) was added and the mixture heated at reflux under argon overnight. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (8% ethyl acetate in hexane) to give 7.08 g of 4-dimethylamino-3-(3,5,5,8,7-pentamethyl-5,6,7,8-tetrahydronaphtalen-2-yl) benzaldehyde (92%). 1H NMR (300 MHz; DMSO) 1.22 (s, 3H); 1.28 (s, 3H); 1.29 (s, 3H); 1.31 (s, 3H); 1.69 (s, 4H); 2.07 (s, 3H); 2.64 (s, 6H); 6.93 (d, J=8.4 Hz, 1H); 7.13 (s, 1H); 7.15 (s, 1H); 7.58 (d, J=2.4 Hz, 1H); 7.75 (dd, J1=8.7 Hz, J2=2.1 Hz, 1H); 9.80 (s, 1H). The solution was degased with argon for 30 minutes the mixture heated at reflux under argon overnight washed successively with water and brine dried over anhydrous magnesium sulfate filtered evaporated The residue was chromatographed on silica gel (8% ethyl acetate in hexane)