2,3-Dibromophenol

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromo-phenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min. was extracted with ethyl acetate (4×100 mL) The pooled organic phases were washed twice with water (30 mL) dried evaporated in vacuo The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3)

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromo-phenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min. was extracted with ethyl acetate (4×100 mL) The pooled organic phases were washed twice with water (30 mL) dried evaporated in vacuo The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Chloro-4-mercapto-phenoxy)-acetic acid ethyl ester (3 g; 12.16 mmol), dibromo-phenol (3.67 g; 14.59 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.45 g; 0.49 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.40 g; 0.73 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (6.74 mL, 48.64 mmol) and NMP (10 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 100° C. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution. The organic phase was dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1)). Yield 1.8 g. HPLC-MS: m/z: 441.2 (M+Na); Rt: 2.34 min. The reaction mixture was extracted with ethyl acetate the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution The organic phase was dried evaporated in vacuo The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1))

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2-liter 4-neck flask equipped with a -10° C. Friedrichs condenser, thermometer, mechanical stirrer, and 0.16 centimeter in diameter dip tube are added 180 grams (0.79 moles) of bisphenol-A and 880 mL of methanol containing 4 wt. % water. Bromine (513 grams, 3.2 moles) was fed with a peristaltic pump to a 1.8 meter, 0.63 centimeter outside diameter teflon tube held in hot water which was maintained at a temperature of >80° C. Bromine vapor thus generated was fed to the reaction flask over a 52 minute period and the temperature was maintained during the ({reaction at 28-32° C. by use of an ice bath. When all of the bromine had been added, additional methanol (175 mL) containing 4 wt. % water was added to the reaction flask and the mixture was stirred at 30° C. The overall methanol to bisphenol-A ratio was 32 moles of methanol per mole of bisphenol-A. A first sample of the homogenous mixture was taken 60 minutes after the bromine was added. The first sample was analyzed and indicated the presence of 0.03% yield of dibromophenol, 0.03% hydrolyzable impurities, 2.79% tribromobisphenol-A, and 97.18% tetrabromobisphenol-A. After an additional 30 minutes, a sample of liquid portion of the heterogenous mixture was analyzed and contained 2.17% tribromobisphenol-A. Water (700 mL) addition was begun immediately after taking the second sample and was complete in 20 minutes. The resulting orange mixture was filtered and the tetrabromobisphenol-A product was washed with 500 mL of deionized water. The product, thus isolated, was placed in a crystallizing dish and 1 mL of 56 wt % HBr was added. The product was then oven dried at 130° C for four hours. The dried product was analyzed as in Example 2 and indicated 99.24 wt. % tetrabromobisphenol-A, an acetone color of 10 APHA, a TOHTO color of 20 APHA, an ionic bromide content of 0 ppm, and a hydrolyzable bromide content of 21 ppm. To a 2-liter 4-neck flask equipped with a -10° C was maintained at a temperature of >80° C the temperature was maintained during the ( {reaction at 28-32° C. by use of an ice bath was added to the reaction flask

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromophenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min. was extracted with ethyl acetate (4×100 mL) The pooled organic phases were washed twice with water (30 mL) dried evaporated in vacuo The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Chloro-4-mercapto-phenoxy)-acetic acid ethyl ester (3 g; 12.16 mmol), dibromophenol (3.67 g; 14.59 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.45 g; 0.49 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocenE (0.40 g; 0.73 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (6.74 mL, 48.64 mmol) and NMP (10 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 100° C. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution. The organic phase was dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1)). Yield 1.8 g. HPLC-MS: m/z: 441.2 (M+Na); Rt: 2.34 min. The reaction mixture was extracted with ethyl acetate the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution The organic phase was dried evaporated in vacuo The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1))

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromophenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane: ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min. was extracted with ethyl acetate (4×100 mL) The pooled organic phases were washed twice with water (30 mL) dried evaporated in vacuo The crude reaction product was purified by flash chromatography (heptane: ethyl acetate (10:1→7:3)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Chloro-4-mercapto-phenoxy)-acetic acid ethyl ester (3 g; 12.16 mmol), dibromophenol (3.67 g; 14.59 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.45 g; 0.49 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocenE (0.40 g; 0.73 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (6.74 mL, 48.64 mmol) and NMP (10 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 100° C. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution. The organic phase was dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane: ethyl acetate (1:1)). Yield 1.8 g. HPLC-MS: m/z: 441.2 (M+Na); Rt: 2.34 min. The reaction mixture was extracted with ethyl acetate the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution The organic phase was dried evaporated in vacuo The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane: ethyl acetate (1:1))

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromo-phenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min. was extracted with ethyl acetate (4×100 mL) The pooled organic phases were washed twice with water (30 mL) dried evaporated in vacuo The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Chloro-4-mercapto-phenoxy)-acetic acid ethyl ester (3 g; 12.16 mmol), dibromo-phenol (3.67 g; 14.59 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.45 g; 0.49 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.40 g; 0.73 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (6.74 mL, 48.64 mmol) and NMP (10 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 100° C. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution. The organic phase was dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1)). Yield 1.8 g. HPLC-MS: m/z: 441.2 (M+Na); Rt: 2.34 min. The reaction mixture was extracted with ethyl acetate the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution The organic phase was dried evaporated in vacuo The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1))