5-Bromo-2-chlorophenylboronic acid

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

Procedure: Following the method described in Example 81, 4-bromo-1-chloro-2-iodo-benzene, isopropylmagnesium chloride and trimethylborate provided 5-bromo-2-chloro-phenylboronic acid (36% yield).

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

Procedure: Following the method described in Example 81, 4-bromo-1-chloro-2-iodo-benzene, isopropylmagnesium chloride and trimethylborate provided 5-bromo-2-chloro-phenylboronic acid (36% yield).

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

Procedure: Following the method described in Example 81, 4-bromo-1-chloro-2-iodo-benzene, isopropylmagnesium chloride and trimethylborate provided 5-bromo-2-chloro-phenylboronic acid (36% yield).

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of lead tetraacetate (26.83 g, 61 mmol) and mercuric diacetate (0.77 g, 2.4 mmol), thoroughly flushed with nitrogen, is added anhydrous chloroform (50 ml) and the reaction mixture is stirred and heated to 40° C. 5-Bromo-2-chlorophenylboronic acid (11.39 g, 48 mmol) is added in one portion, and the reaction mixture is stirred at 40° C. for 4 hours. After cooling to room temperature potassium carbonate (3.34 g) is added, the mixture stirred vigorously for 5 minutes and then filtered. The filtrate is concentrated in vacuo to give 5-bromo-2-chlorophenyllead triacetate (25.33 g), used without further purification in the next step. thoroughly flushed with nitrogen is added anhydrous chloroform (50 ml) the reaction mixture is stirred at 40° C. for 4 hours is added the mixture stirred vigorously for 5 minutes filtered The filtrate is concentrated in vacuo

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

Procedure: 4-Bromo-1-chloro-2-iodobenzene (10.35 g, 33 mmol) is dissolved in anhydrous tetrahydrofuran (60 ml) and the solution is cooled to −75° C. under an atmosphere of argon. Isopropylmagnesium chloride (17.1 ml, 34 mmol, 2M solution in tetrahydrofuran) is added dropwise over 30 minutes, maintaining the internal temperature below −70° C. by external cooling. Once the addition is complete, the reaction mixture is stirred at approximately −70° C. for 30 minutes and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture is then cooled to −78° C. and trimethyl borate (7.3 ml, 65 mmol) is added dropwise. The mixture is stirred at −78° C. for 30 minutes and then the cooling bath is removed and the mixture is stirred at room temperature for 1.5 hours. 2M Aqueous hydrochloric acid (30 ml) is added, and the crude product is extracted with ethyl acetate. The organic phase is washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. Trituration with hexane gives 5-bromo-2-chlorophenylboronic acid (6.16 g) as an off-white solid. maintaining the internal temperature below −70° C. by external cooling Once the addition to warm to room temperature stirred for 1 hour The reaction mixture is then cooled to −78° C. The mixture is stirred at −78° C. for 30 minutes the cooling bath is removed the mixture is stirred at room temperature for 1.5 hours 2M Aqueous hydrochloric acid (30 ml) is added the crude product is extracted with ethyl acetate The organic phase is washed with water and brine dried over anhydrous magnesium sulfate filtered the filtrate evaporated in vacuo

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of lead tetraacetate (1.46 g, 3.3 mmol) and mercuric diacetate (42 mg, 0.13 mmol), thoroughly flushed with nitrogen, is added anhydrous chloroform (2.5 ml) is introduced and the reaction mixture is stirred and heated to 40° C. 5-Bromo-2-chlorophenylboronic acid (0.62 g, 2.6 mmol) is added in one portion, and the reaction mixture is stirred at 40° C. for 4 hours. After cooling to room temperature potassium carbonate (0.18 g) is added, the mixture stirred vigorously for 5 minutes and then filtered. The filtrate is concentrated in vacuo to give 5-bromo-2-chlorophenyllead triacetate (1.23 g), used without further purification in the next step. thoroughly flushed with nitrogen is added anhydrous chloroform (2.5 ml) is introduced the reaction mixture is stirred at 40° C. for 4 hours is added the mixture stirred vigorously for 5 minutes filtered The filtrate is concentrated in vacuo

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

Procedure: 4-Bromo-1-chloro-2-iodobenzene (10.35 g, 33 mmol) is dissolved in anhydrous tetrahydrofuran (60 ml) and the solution is cooled to −75° C. under an atmosphere of argon. Isopropylmagnesium chloride (17.1 ml, 34 mmol, 2M solution in tetrahydrofuran) is added dropwise over 30 minutes, maintaining the internal temperature below −70° C. by external cooling. Once the addition is complete, the reaction mixture is stirred at approximately −70° C. for 30 minutes and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture is then cooled to −78° C. and trimethyl borate (7.3 ml, 65 mmol) is added dropwise. The mixture is stirred at −78° C. for 30 minutes and then the cooling bath is removed and the mixture stirred at room temperature for 1.5 hours. 2M Aqueous hydrochloric acid (30 ml) is added, and the crude product is then extracted with ethyl acetate. The organic phase is washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. Trituration with hexane gives 5-bromo-2-chlorophenylboronic acid (6.16 g) as an off-white solid. maintaining the internal temperature below −70° C. by external cooling Once the addition to warm to room temperature stirred for 1 hour The reaction mixture is then cooled to −78° C. The mixture is stirred at −78° C. for 30 minutes the cooling bath is removed the mixture stirred at room temperature for 1.5 hours 2M Aqueous hydrochloric acid (30 ml) is added the crude product is then extracted with ethyl acetate The organic phase is washed with water and brine dried over anhydrous magnesium sulfate filtered the filtrate evaporated in vacuo

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

Procedure: 4-Bromo-1-chloro-2-iodobenzene (10.35 g, 33 mmol) is dissolved in anhydrous tetrahydrofuran (60 ml) and the solution is cooled to −75° C. under an atmosphere of argon. Isopropylmagnesium chloride (17.1 ml, 34 mmol, 2M solution in tetrahydrofuran) is added dropwise over 30 minutes, maintaining the internal temperature below −70° C. by external cooling. Once the addition is complete, the reaction mixture is stirred at approximately −70° C. for 30 minutes and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture is then cooled to −78° C. and trimethyl borate (7.3 ml, 65 mmol) is added dropwise. The mixture is stirred at −78° C. for 30 minutes and then the cooling bath is removed and the mixture stirred at room temperature for 1.5 hours. 2M Aqueous hydrochloric acid (30 ml) is added, and the crude product is then extracted with ethyl acetate. The organic phase is washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. Trituration with hexane gives 5-bromo-2-chlorophenylboronic acid (6.16 g) as an off-white solid. maintaining the internal temperature below −70° C. by external cooling Once the addition to warm to room temperature stirred for 1 hour The reaction mixture is then cooled to −78° C. The mixture is stirred at −78° C. for 30 minutes the cooling bath is removed the mixture stirred at room temperature for 1.5 hours 2M Aqueous hydrochloric acid (30 ml) is added the crude product is then extracted with ethyl acetate The organic phase is washed with water and brine dried over anhydrous magnesium sulfate filtered the filtrate evaporated in vacuo