N-(2-bromophenyl)acetamide

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

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

Conditions: temp:70.01; pressure:0.00; stir:

Procedure: Following general procedure F using 2‐bromoacetanilide (53.5 mg, 0.25 mmol), B2pin2 (127 mg, 0.50 mmol), [Ir(COD)OMe]2 (2.5 mg, 0.00375 mmol) and 1a (3.8 mg, 0.0075 mmol) in THF (1.25 mL). The reaction was stirred at 70 °C for 20 hours before cooling and the solvents removed. Analysis of crude 1 H NMR using internalstandard 1,2‐dimethoxyethane showed 1:1.4 meta:para borylation in 65% yield. The crude product was purified by silica gel chromatography (Pet. Ether (40‐60):EtOAc (19:1‐6:4) to give the title compound (as a 1:1.7:1.3 mixture of meta:para:SM ratio, as determined by 1 H NMR) as a colourless oil. NMR yields have been used for all comparisons.

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

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

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

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

Procedure: 440 mg of sodium hydride solution (concentration 40%) was added portionwise to 30 ml of ethylene glycol. After abating of the froth occurred, 50 mg of cuprous chloride, 75 mg of 8-hydroxyquinoline and 1.07 g of 2-bromo-1-acetylamino-benzene were added to the solution and the mixture was heated at 70° to 80° C. for 50 minutes. The reaction mixture was treated in a usual manner, and then crystallization was effected from a solvent mixture of n-hexane and ethyl acetate to give 720 mg of the desired compound. Yield: 74%, melting point: 89°-91° C. the mixture was heated at 70° to 80° C. for 50 minutes The reaction mixture was treated in a usual manner crystallization was effected from a solvent mixture of n-hexane and ethyl acetate

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

Procedure: 2.3 ml of a 28% solution of sodium methoxide in methanol and 63 mg of copper powder were added to 40 ml of methanol, and the mixture was heated under reflux for 1 hour. Then, 145 mg of 8-hydroxyquinoline and 2.14 g of 2-bromo-1-acetylaminobenzene were added thereto, and the mixture was heated under reflux for 3 hours. The reaction mixture was treated in a usual manner, to obtain 1.43 g (yield: 87%) of the desired compound. the mixture was heated under reflux for 1 hour the mixture was heated under reflux for 3 hours The reaction mixture was treated in a usual manner

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

Procedure: 2.3 ml of a 28% solution of sodium methoxide in methanol and 63 mg of copper powder were added to 40 ml of methanol, and the mixture was heated under reflux for 1 hour. Then, 145 mg of 8-hydroxyquinoline and 2.14 g of 2-bromo-1-acetylaminobenzene were added thereto, and the mixture was heated under reflux for 3 hours. The reaction mixture was treated in a usual manner, to obtain 1.43 g (yield: 87%) of the desired compound. the mixture was heated under reflux for 1 hour the mixture was heated under reflux for 3 hours The reaction mixture was treated in a usual manner

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

Procedure: Then, 2.14 g of the 2-bromo-1-acetylaminobenzene was added to a solution containing 2.3 ml of a 28% methanol solution of sodium methoxide, 100 mg of cuprous chloride, and 145 mg of 8-hydroxyquinoline in 40 ml of methanol, and the mixture was heated under reflux for 50 minutes. After cooling with water, ethyl acetate was added thereto, and the resulting mixture was washed with water and dried over Glauber's salt. The solvent was distilled off, and the obtained crude crystals were recrystallized from an n-hexane/ethyl acetate solvent mixture, to obtain 1.56 g (yield: 95%) of the desired compound. The spectrum data of the compound was in agreement with the spectrum data of the separately synthesized reference compound. the mixture was heated under reflux for 50 minutes was added the resulting mixture was washed with water dried over Glauber's salt The solvent was distilled off the obtained crude crystals were recrystallized from an n-hexane/ethyl acetate solvent mixture

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

Procedure: 2-Bromo-1-acetylaminobenzene was synthesized in the usual manner from 2-bromoaniline. That is, 150 ml of acetonitrile was added to 25.0 g of 2-bromoaniline, then 15.1 ml of glacial acetic acid was added thereto, and the reaction mixture was heated under reflux for 2 hours. After bringing its temperature to room temperature, 300 ml of ethyl acetate was added thereto, and after the resulting mixture was washed with water twice, the solvent was distilled off, and recrystallization of the crude crystals from a hexane/ethyl acetate solvent mixture was carried out, to obtain 23.2 g (yield: 75%) of 2-bromo-1-acetylaminobenzene. the reaction mixture was heated under reflux for 2 hours to room temperature after the resulting mixture was washed with water twice the solvent was distilled off recrystallization of the crude crystals from a hexane/ethyl acetate solvent mixture

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

Procedure: 2-Bromo-1-acetylaminobenzene was synthesized in the usual manner from 2-bromoaniline. That is, 150 ml of acetonitrile was added to 25.0 g of 2-bromoaniline, then 15.1 ml of glacial acetic acid was added thereto, and the reaction mixture was heated under reflux for 2 hours. After bringing its temperature to room temperature, 300 ml of ethyl acetate was added thereto, and after the resulting mixture was washed with water twice, the solvent was distilled off, and recrystallization of the crude crystals from a hexane/ethyl acetate solvent mixture was carried out, to obtain 23.2 g (yield: 75%) of 2-bromo-1-acetylaminobenzene. the reaction mixture was heated under reflux for 2 hours to room temperature after the resulting mixture was washed with water twice the solvent was distilled off recrystallization of the crude crystals from a hexane/ethyl acetate solvent mixture