3-bromo-2-methoxyaniline

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3-Bromo-2-methoxy-phenylamine (10 g, 0.05 mol), NH2OH.H2SO4 (48.73 g, 0.3 mol), conc. HCl (5 mL) in H2O (50 mL) is slowly added to the solution of chloral hydrate (9 g, 0.05 mol), Na2SO4 (42.18 g, 0.3 mol) in H2O (200 mL) then stirred at 35° C. for 1 h, 52° C. for 1.5 h, 75° C. for 1 h. After the reaction, the mixture is filtered and the solid is dried under vacuum to give the desired compound. After the reaction the mixture is filtered the solid is dried under vacuum

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3-Bromo-2-methoxy-phenylamine (10 g, 0.05 mol), NH2OH.H2SO4 (48.73 g, 0.3 mol), conc. HCl (5 mL) in H2O (50 mL) is slowly added to the solution of chloral hydrate (9 g, 0.05 mol), Na2SO4 (42.18 g, 0.3 mol) in H2O (200 mL) then stirred at 35° C. for 1 h, 52° C. for 1.5 h, 75° C. for 1 h. After the reaction, the mixture is filtered and the solid is dried under vacuum to give the desired compound. After the reaction the mixture is filtered the solid is dried under vacuum

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1-Bromo-2-methoxy-3-nitro-benzene (17.8 g, 0.0768 mol), SnCl2 (69.27 g, 0.3069 mol) and 4N HCl (80 mL) in THF (200 mL) is stirred at 80° C. for 16 h. After reaction, evaporated out THF and added NaHCO3 solution, filtered and the filtrate is extracted with ethyl acetate (3×800 mL). The combined organic phase is ished with water and brine, dried over Na2SO4, concentrated in vacuo to give the desired product. Yield: 14.8 g (96%). After reaction evaporated out THF added NaHCO3 solution filtered the filtrate is extracted with ethyl acetate (3×800 mL) dried over Na2SO4 concentrated in vacuo

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1-Bromo-2-methoxy-3-nitro-benzene (17.8 g, 0.0768 mol), SnCl2 (69.27 g, 0.3069 mol) and 4N HCl (80 mL) in THF (200 mL) is stirred at 80° C. for 16 h. After reaction, evaporated out THF and added NaHCO3 solution, filtered and the filtrate is extracted with ethyl acetate (3×800 mL). The combined organic phase is ished with water and brine, dried over Na2SO4, concentrated in vacuo to give the desired product. Yield: 14.8 g (96%). After reaction evaporated out THF added NaHCO3 solution filtered the filtrate is extracted with ethyl acetate (3×800 mL) dried over Na2SO4 concentrated in vacuo

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

Procedure: To a stirred solution of 3-bromo-2-methoxyaniline (10 g) in ethyl acetate (100 mL) was added concentrated hydrochloric acid (7 mL) at about room temperature. The reaction mixture was stirred for about 2 hours and filtered to give a solid, which was washed with ethyl acetate and dried at about 50° C. to about 55° C. Yield: 10 g filtered to give a solid, which was washed with ethyl acetate dried at about 50° C. to about 55° C

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

Procedure: A mixture of 3-bromo-2-methoxyaniline (3 g), 3-carboxyphenylboronic acid (2.94 g), bis(triphenylphosphine)palladium(II)chloride [PdCl2(PPh3)2] (0.30 g) and potassium carbonate (5.2 g) in ethanol (100 mL) and water (20 mL) was heated to about reflux temperature and stirred for about 28 hours. The hot mixture was filtered to remove the catalyst. The clear filtrate was concentrated under vacuum. To the residue, water (50 mL) and methanol (50 mL) was added, acidified to pH 3-5 using hydrochloric acid and stirred for about 30 minutes at about room temperature. The slurry was filtered, washed with n-hexane (50 mL) and dried in an oven at about 55° C. to about 60° C. for about 12 hours. Yield: 1.8 g was heated to about reflux temperature The hot mixture was filtered to remove the catalyst The clear filtrate was concentrated under vacuum To the residue, water (50 mL) and methanol (50 mL) was added stirred for about 30 minutes at about room temperature The slurry was filtered washed with n-hexane (50 mL) dried in an oven at about 55° C. to about 60° C. for about 12 hours

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

Procedure: To a stirred solution of 3-bromo-2-methoxyaniline (10 g) in ethyl acetate (100 mL) was added concentrated hydrochloric acid (7 mL) at about room temperature. The reaction mixture was stirred for about 2 hours and filtered to give a solid, which was washed with ethyl acetate and dried at about 50° C. to about 55° C. Yield: 10 g filtered to give a solid, which was washed with ethyl acetate dried at about 50° C. to about 55° C

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

Procedure: A mixture of 3-bromo-2-methoxyaniline (3 g), 3-carboxyphenylboronic acid (2.94 g), bis(triphenylphosphine)palladium(II)chloride [PdCl2(PPh3)2] (0.30 g) and potassium carbonate (5.2 g) in ethanol (100 mL) and water (20 mL) was heated to about reflux temperature and stirred for about 28 hours. The hot mixture was filtered to remove the catalyst. The clear filtrate was concentrated under vacuum. To the residue, water (50 mL) and methanol (50 mL) was added, acidified to pH 3-5 using hydrochloric acid and stirred for about 30 minutes at about room temperature. The slurry was filtered, washed with n-hexane (50 mL) and dried in an oven at about 55° C. to about 60° C. for about 12 hours. Yield: 1.8 g was heated to about reflux temperature The hot mixture was filtered to remove the catalyst The clear filtrate was concentrated under vacuum To the residue, water (50 mL) and methanol (50 mL) was added stirred for about 30 minutes at about room temperature The slurry was filtered washed with n-hexane (50 mL) dried in an oven at about 55° C. to about 60° C. for about 12 hours

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

Procedure: To an ice cooled solution of 6-bromo-2-anisidine (1.01 g, 5 mmol) in methylene chloride (30 mL) was slowly added a 1.0 M solution of boron tribromide in methylene chloride (10 mL, 10 mmol) via syringe. The reaction was slowly warmed to room temperature and stirred overnight. Methanol (10 mL) was added and the solvents removed by rotoevaporation to give the title compound (0.87 g, 92% yield). the solvents removed by rotoevaporation

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

Procedure: To a cooled solution of 2-anisidine (2.7 mL, 23.7 mmol) in cetic acid (20 mL) at 10° C. was slowly added a solution of bromine (1.22 mL, 23.7 mmol) in acetic acid (10 mL) over a 10 min period. After stirring for 10 min, the solvents were removed by rotoevaporation and the residue dissolved in ethyl acetate. This solution was successively washed with saturated sodium bicarbonate solution and dried over anhydrous magnesium sulfate. After filtering, the solvents were removed by rotoevaporation and the product purified by flash column chromatography on silica gel eluted with 45% methylene chloride in hexanes to yield 3.44 g (72% yield) of the title compound. the solvents were removed by rotoevaporation the residue dissolved in ethyl acetate This solution was successively washed with saturated sodium bicarbonate solution dried over anhydrous magnesium sulfate After filtering the solvents were removed by rotoevaporation the product purified by flash column chromatography on silica gel eluted with 45% methylene chloride in hexanes

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3-Bromo-2-methoxy-phenylamine (10 g, 0.05 mol), NH2OH.H2SO4 (48.73 g, 0.3 mol), conc. HCl (5 mL) in H2O (50 mL) is slowly added to the solution of chloral hydrate (9 g, 0.05 mol), Na2SO4 (42.18 g, 0.3 mol) in H2O (200 mL) then stirred at 35° C. for 1 h, 52° C. for 1.5 h, 75° C. for 1 h. After the reaction, the mixture is filtered and the solid is dried under vacuum to give the desired compound. After the reaction the mixture is filtered the solid is dried under vacuum

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1-Bromo-2-methoxy-3-nitro-benzene (17.8 g, 0.0768 mol), SnCl2 (69.27 g, 0.3069 mol) and 4N HCl (80 mL) in THF (200 mL) is stirred at 80° C. for 16 h. After reaction, evaporated out THF and added NaHCO3 solution, filtered and the filtrate is extracted with ethyl acetate (3×800 mL). The combined organic phase is ished with water and brine, dried over Na2SO4, concentrated in vacuo to give the desired product. Yield: 14.8 g (96%). After reaction evaporated out THF added NaHCO3 solution filtered the filtrate is extracted with ethyl acetate (3×800 mL) dried over Na2SO4 concentrated in vacuo