tert-butyl 2-bromobenzoate

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: A solution of o-bromobenzoic acid (1 g), N, N'-dicyclohexyl carbodiimide (1.129 g), t-butanol (405 mg) and 4-dimethylaminopyridine (61 mg) in dry ether (20 ml) was stirred at room temperature for 18 h. The resulting precipitate was filtered off and the filtrate evaporated to give a colourless solid which was triturated under petroleum ether (40°-600°) (20 ml) and filtered. The filtrate was evaporated to give a pale yellow oil (0,994 g). b.p. 80°-84°/0.35 mmHg. The resulting precipitate was filtered off the filtrate evaporated to give a colourless solid which was triturated under petroleum ether (40°-600°) (20 ml) filtered The filtrate was evaporated

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

Procedure: A solution of o-bromobenzoic acid (1 g), N, N'-dicyclohexyl carbodiimide (1.129 g), t-butanol (405 mg) and 4-dimethylaminopyridine (61 mg) in dry ether (20 ml) was stirred at room temperature for 18 h. The resulting precipitate was filtered off and the filtrate evaporated to give a colourless solid which was triturated under petroleum ether (40°-600°) (20 ml) and filtered. The filtrate was evaporated to give a pale yellow oil (0,994 g). b.p. 80°-84°/0.35 mmHg. The resulting precipitate was filtered off the filtrate evaporated to give a colourless solid which was triturated under petroleum ether (40°-600°) (20 ml) filtered The filtrate was evaporated

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

Procedure: 51.4 g of Bromobenzoic acid tert.-butyl ester, 21.6 g of trimethylsilylacetylene, 1.4 g of (Ph3P)2PdCl2 in 400 ml of absolute acetonitrile and 100 ml of triethylamine are stirred under reflux for 8 hours in an atmosphere of nitrogen. After the reaction product has been worked up with CH2Cl2 /H2O and distilled, 40.6 g of 4-(trimethylsilylethinyl)-benzoic acid tert.-butyl ester are obtained. under reflux for 8 hours in an atmosphere of nitrogen distilled

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

Procedure: 51.4 g of Bromobenzoic acid tert.-butyl ester, 21.6 g of trimethylsilylacetylene, 1.4 g of (Ph3P)2PdCl2 in 400 ml of absolute acetonitrile and 100 ml of triethylamine are stirred under reflux for 8 hours in an atmosphere of nitrogen. After the reaction product has been worked up with CH2Cl2 /H2O and distilled, 40.6 g of 4-(trimethylsilylethinyl)-benzoic acid tert.-butyl ester are obtained. under reflux for 8 hours in an atmosphere of nitrogen distilled

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound A (22.8 g, 88.6 mmol) and 2-fluoro-4-methylphenylboronic acid (15.0 g, 97.4 mmol) were suspended in isopropyl alcohol (75 mL, 980 mmol). A solution of sodium carbonate (16 g, 150 mmol) in water (75 mL, 4.2 mol) was added and the mixture was degassed under nitrogen. Tetrakis(triphenylphosphine)palladium(0) (1.0 g, 880 μmol) was then added and the mixture was stirred at 90° C. overnight. The mixture was cooled to room temperature, EtOAc (200 mL) and water (200 mL) were added, and the mixture was filtered. The liquor was extracted with EtOAc (2×100 mL), washed with saturated aqueous NaCl, dried over MgSO4, filtered and concentrated. The material was purified by flash chromatography (0-15% EtOAc in hexanes) to yield compound B as a colorless oil (14.9 g, 96% purity). the mixture was degassed under nitrogen The mixture was cooled to room temperature the mixture was filtered The liquor was extracted with EtOAc (2×100 mL) washed with saturated aqueous NaCl dried over MgSO4 filtered concentrated The material was purified by flash chromatography (0-15% EtOAc in hexanes)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Bromobenzoic acid (203.2 g, 1011 mmol) was added to a solution of 1.0 M DCC in DCM (1011 mL, 1011 mmol) and cooled at 0° C. DMAP (11.36 g, 93.0 mmol) and t-butyl alcohol (106.3 mL, 1112 mmol) were added and the mixture was stirred at room temperature for 10 minutes, then warmed to room temperature and stirred overnight. The mixture was then filtered, washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl, dried over MgSO4, filtered and concentrated under reduced pressure to yield compound A as a clear oil (168.4 g). warmed to room temperature stirred overnight The mixture was then filtered washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl dried over MgSO4 filtered concentrated under reduced pressure

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Bromobenzoic acid (203.2 g, 1011 mmol) was added to a solution of 1.0 M DCC in DCM (1011 mL, 1011 mmol) and cooled at 0° C. DMAP (11.36 g, 93.0 mmol) and t-butyl alcohol (106.3 mL, 1112 mmol) were added and the mixture was stirred at room temperature for 10 minutes, then warmed to room temperature and stirred overnight. The mixture was then filtered, washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl, dried over MgSO4, filtered and concentrated under reduced pressure to yield compound A as a clear oil (168.4 g). warmed to room temperature stirred overnight The mixture was then filtered washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl dried over MgSO4 filtered concentrated under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound A (80.0 g, 311 mmol) and 3-fluoro-4-methylphenylboronic acid (52.7 g, 342 mmol) were suspended in isopropyl alcohol (260 mL, 3.5 mol). A solution of sodium carbonate (56.1 g, 529 mmol) in water (260 mL, 15 mol) was added and the mixture was degassed under nitrogen. Tetrakis(triphenylphosphine)palladium(0) (3.6 g, 3.1 mmol) was then added and the mixture was stirred at 90° C. for 17 hours. The mixture was concentrated under reduced pressure and suspended in water (200 mL). The aqueous phase was extracted with EtOAc (600 mL) and separated. The organic phase was washed with saturated aqueous NaCl and concentrated under reduced pressure. The recovered oil was purified by silica gel chromatography (4-6% 5×120 g column) to yield compound B as a clear oil (68.2 g). the mixture was degassed under nitrogen The mixture was concentrated under reduced pressure The aqueous phase was extracted with EtOAc (600 mL) separated The organic phase was washed with saturated aqueous NaCl concentrated under reduced pressure The recovered oil was purified by silica gel chromatography (4-6% 5×120 g column)

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

Procedure: To a solution of DCC (32.8 g, 159 mmol) in DCM (200 mL, 2 mol) was added 2-bromobenzoic acid (32.0 g, 159 mmol) followed by DMAP (1.8 g, 15 mmol) and t-butyl alcohol (15.2 mL, 159 mmol). The mixture was stirred at room temperature for 16 hours, then filtered. The organic was washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl, dried over MgSO4, filtered and concentrated under reduced pressure to yield compound A as an oil (41.6 g). filtered The organic was washed with saturated NaHCO3 (200 mL), saturated aqueous NaCl dried over MgSO4 filtered concentrated under reduced pressure