2-(2-bromophenyl)acetaldehyde

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

Procedure: To a solution of 10.0 grams (0.05 mole) of 2-(2-bromophenyl)acetaldehyde (from the above preparation and another similar preparation) in 50 milliliters of dry methanol, was added 50 milliliters of trimethyl orthoformate and 0.25 gram of p-toluenesulfonic acid monohydrate and the resulting mixture was heated at reflux temperature for 3.5 hours. At the end of this period, the reaction mixture was cooled and 100 milliliters of diethyl ether and 50 milliliters of a 1:1 solution of 50 percent aqueous sodium hydroxide/brine were added. The ether solution was mechanically separated, washed, dried and stripped on the rotary evaporator to obtain 2-(2-bromophenyl)acetaldehyde dimethylacetal intermediate as a yellow oil. The latter was distilled to obtain 10.5 grams (85 percent yield) of purified product as a clear oil, b.p. 65°-67° /0.2 mm. the resulting mixture was heated at reflux temperature for 3.5 hours At the end of this period, the reaction mixture was cooled The ether solution was mechanically separated washed dried stripped on the rotary evaporator

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

Procedure: A solution of 9.11 grams (0.045 mole) of 2-(2-bromophenyl)ethanol in 35 milliliters of methylene chloride was added to a stirred suspension of 14.62 grams (0.063 mole) of pyridinium chlorochromate in 75 milliliters of methylene chloride at ambient temperature whereupon a slightly exothermic reaction took place with the formation of a black reaction mixture. Stirring was continued for 15 hours at ambient temperature; then 150 milliliters of ether was added and the mixture filtered through silica gel on a pad of celite. The insoluble residue was washed with 100 milliliters of ether, filtered, the ether solutions combined and the solvents evaporated on a rotary evaporator to recover as residue, 8.0 grams (90 percent) of the desired 2-(2-bromophenyl)acetaldehyde intermediate as an oil. The oil had an Rf of 0.6 on silica gel when eluted with one percent methanol in chloroform. the mixture filtered through silica gel on a pad of celite The insoluble residue was washed with 100 milliliters of ether filtered the solvents evaporated on a rotary evaporator to recover as residue eluted with one percent methanol in chloroform

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

Procedure: A solution of 9.11 grams (0.045 mole) of 2-(2-bromophenyl)ethanol in 35 milliliters of methylene chloride was added to a stirred suspension of 14.62 grams (0.063 mole) of pyridinium chlorochromate in 75 milliliters of methylene chloride at ambient temperature whereupon a slightly exothermic reaction took place with the formation of a black reaction mixture. Stirring was continued for 15 hours at ambient temperature; then 150 milliliters of ether was added and the mixture filtered through silica gel on a pad of celite. The insoluble residue was washed with 100 milliliters of ether, filtered, the ether solutions combined and the solvents evaporated on a rotary evaporator to recover as residue, 8.0 grams (90 percent) of the desired 2-(2-bromophenyl)acetaldehyde intermediate as an oil. The oil had an Rf of 0.6 on silica gel when eluted with one percent methanol in chloroform. the mixture filtered through silica gel on a pad of celite The insoluble residue was washed with 100 milliliters of ether filtered the solvents evaporated on a rotary evaporator to recover as residue eluted with one percent methanol in chloroform

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

Procedure: The title compound was prepared from [2-amino-3-(trifluoromethyl)phenyl]-(3-hydroxy-phenyl)methanone and (2-Bromo-phenyl)-acetaldehyde following the procedure of Example 457: MS (ES) m/z 441.8; HRMS: calcd for C22H13BrF3NO+H+, 444.02053; found (ESI, [M+H]+), 444.0191.

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

Procedure: To a solution of 2-(2-bromophenyl) acetaldehyde (15 g, 75.37 mmol) in THF (100 ml) was added propyl magnesium bromide (1.0 M in THF) (15.13 g, 113.6 mmol) at 0° C. then stirred at RT for 3 h. The reaction mixture was quenched with ammonium chloride then the title compound was purified by separation methods A, E and M. (Yield 7.0 g). The enantiomer showed up at tr=13.6 min with Chiralcel OJH (4.6×250 mm) 5μ, hexane:ethanol (98:02), 1 ml/min. The reaction mixture was quenched with ammonium chloride the title compound was purified by separation methods A, E and M showed up at tr=13.6 min with Chiralcel OJH (4.6×250 mm) 5μ, hexane:ethanol (98:02), 1 ml/min.

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

Procedure: To a solution of 2-(2-bromophenyl)acetaldehyde (16 g, 80.8 mmol) in THF (100 ml) was added propyl magnesium bromide (48 ml (2.0 M) in THF), 97 mmol) at 0° C. then stirred at room temperature for 5 h. The reaction mixture was quenched with ammonium chloride then the title compound was purified by separation methods A, E and H. (Yield 740 mg). The enantiomer-2 showed up at tr=5.70 min with Chiralcel OD-H (4.6×250 mm) 5μ, hexane:2-PrOH:TFA (90:5:0.1), 1 ml/min. The reaction mixture was quenched with ammonium chloride the title compound was purified by separation methods A, E and H showed up at tr=5.70 min with Chiralcel OD-H (4.6×250 mm) 5μ, hexane:2-PrOH:TFA (90:5:0.1), 1 ml/min.

Conditions: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2,2,2-trifluoroethanamine hydrochloride (27.1 g, 200 mmol) in DCM (400 ml) and water (50 ml) was added NaNO2 (15.43 g, 241 mmol) at 0° C. and stirred for 1 h. Then cooled to 78° C. then added 2-(2-bromophenyl)acetaldehyde (20 g, 100 mmol) and ZrCl4 (30.4 g, 130 mmol) and stirred for 2 h. The reaction mixture was quenched with MeOH (30 ml). The title compound was purified by separation methods A and E. (Yield 13.0 g). The reaction mixture was quenched with MeOH (30 ml) The title compound was purified by separation methods A and E

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

Procedure: To a solution of 10.0 grams (0.05 mole) of 2-(2-bromophenyl)acetaldehyde (from the above preparation and another similar preparation) in 50 milliliters of dry methanol, was added 50 milliliters of trimethyl orthoformate and 0.25 gram of p-toluenesulfonic acid monohydrate and the resulting mixture was heated at reflux temperature for 3.5 hours. At the end of this period, the reaction mixture was cooled and 100 milliliters of diethyl ether and 50 milliliters of a 1:1 solution of 50 percent aqueous sodium hydroxide/brine were added. The ether solution was mechanically separated, washed, dried and stripped on the rotary evaporator to obtain 2-(2-bromophenyl)acetaldehyde dimethylacetal intermediate as a yellow oil. The latter was distilled to obtain 10.5 grams (85 percent yield) of purified product as a clear oil, b.p. 65°-67° /0.2 mm. the resulting mixture was heated at reflux temperature for 3.5 hours At the end of this period, the reaction mixture was cooled The ether solution was mechanically separated washed dried stripped on the rotary evaporator

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

Procedure: A solution of 9.11 grams (0.045 mole) of 2-(2-bromophenyl)ethanol in 35 milliliters of methylene chloride was added to a stirred suspension of 14.62 grams (0.063 mole) of pyridinium chlorochromate in 75 milliliters of methylene chloride at ambient temperature whereupon a slightly exothermic reaction took place with the formation of a black reaction mixture. Stirring was continued for 15 hours at ambient temperature; then 150 milliliters of ether was added and the mixture filtered through silica gel on a pad of celite. The insoluble residue was washed with 100 milliliters of ether, filtered, the ether solutions combined and the solvents evaporated on a rotary evaporator to recover as residue, 8.0 grams (90 percent) of the desired 2-(2-bromophenyl)acetaldehyde intermediate as an oil. The oil had an Rf of 0.6 on silica gel when eluted with one percent methanol in chloroform. the mixture filtered through silica gel on a pad of celite The insoluble residue was washed with 100 milliliters of ether filtered the solvents evaporated on a rotary evaporator to recover as residue eluted with one percent methanol in chloroform