2-(2-bromophenyl)acetonitrile

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:

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

Procedure: Prepared according to procedure B from 2-bromophenylacetonitrile and (1,4-dihydro4,4-dimethyl-2-oxo-2H-3,1-benzoxazin-6-yl)boronic acid. White solid; mp 176-179° C.; 1H-NMR (DMSO-d6), δ10.31 (s, 1H), 7.53 (m, 1H), 7.48(m,2H), 7.22-7.32(m,3H), 6.98(d,1H; J=8.0 Hz), 3.90(s,2H), 1.64(s,6H). MS (+)APCI [M+H]+m/z =293. Anal. Calc. For C18H16N2O2: C, 73.95, H, 5.52, N, 9.58. Found: C,73.51, H, 5.70, N, 9.39. Prepared

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

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

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

Procedure: To a solution of 0.784 g (4 mmol) 2-bromophenyl-acetonitrile in 16 ml toluene were added 0.8 ml water, 0.412 g (4.8 mmol) cyclopropylboronic acid, 2.97 g (14 mmol) tribasic potassium phosphate, 0.1 12 g (0.4 mmol) tricyclohexylphosphine and 0.045 g (0.2 mmol) palladium(II) acetate. The reaction mixture was stirred at 100° C. for 2 days. The solvent was evaporated and the residue taken up in water and ethyl acetate. The organic layer was washed with brine, dried over MgSO4, filtered and evaporated. The residue was purified using column chromatography (SiO2, heptane/ethyl acetate 98:2) to yield 0.40 g of (2-cyclopropyl-phenyl)-acetonitrile as a light-yellow oil that was used directly for the next step. The solvent was evaporated The organic layer was washed with brine dried over MgSO4 filtered evaporated The residue was purified

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

Procedure: To a solution of 0.784 g (4 mmol) 2-bromophenyl-acetonitrile in 16 ml toluene were added 0.8 ml water, 0.412 g (4.8 mmol) cyclopropylboronic acid, 2.97 g (14 mmol) tribasic potassium phosphate, 0.1 12 g (0.4 mmol) tricyclohexylphosphine and 0.045 g (0.2 mmol) palladium(II) acetate. The reaction mixture was stirred at 100° C. for 2 days. The solvent was evaporated and the residue taken up in water and ethyl acetate. The organic layer was washed with brine, dried over MgSO4, filtered and evaporated. The residue was purified using column chromatography (SiO2, heptane/ethyl acetate 98:2) to yield 0.40 g of (2-cyclopropyl-phenyl)-acetonitrile as a light-yellow oil that was used directly for the next step. The solvent was evaporated The organic layer was washed with brine dried over MgSO4 filtered evaporated The residue was purified

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

Procedure: To a cooled solution of 730.0 g of o-bromophenylacetonitrile in 2.9 l of absolute ethanol is added, dropwise, while stirring, 740 ml of concentrated sulphuric acid. The addition requires about two hours. The reaction mixture is heated under reflux for nine hours, poured into ice water, and extracted with 2.5 l of ether. The ether extracts are washed, dried, and concentrated. The residue is distilled to give 780.0 g of ethyl o-bromophenylacetate, bp. about 115°-117° (4mm), nD26 1,5434. The addition The reaction mixture is heated under reflux for nine hours extracted with 2.5 l of ether The ether extracts are washed dried concentrated The residue is distilled

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

Procedure: To a suspension of 220.0 g of sodium cyanide in 265 ml of water and 380 ml of absolute ethanol, is added, while stirring, a solution of 911.0 g of o-bromobenzyl bromide in 911 ml of ethanol. The reaction proceeds exothermally, but is eventually heated under reflux for about 0.5 hour, then cooled in an ice-bath, and filtered. The solid is washed with ether, the filtrate is concentrated, the residue is suspended in 300 ml of water and extracted with three 500 ml portions of ether. The ether extracts are washed, dried, and the solvent is removed. The residue is distilled to give 730 g of the named product, bp 141°-142° (12mm). is added is eventually heated under reflux for about 0.5 hour cooled in an ice-bath filtered The solid is washed with ether the filtrate is concentrated extracted with three 500 ml portions of ether The ether extracts are washed dried the solvent is removed The residue is distilled

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

Procedure: Into a 500-mL 3-necked round-bottom flask, was placed 2-(2-bromophenyl)acetonitrile (9.8 g, 49.99 mmol, 1.00 equiv), tetrahydrofuran (50 mL). This was followed by the addition of BH3 solution (250 mL, 1N in tetrahydrofuran) dropwise with stiffing at 0° C. The resulting solution was stirred overnight at room temperature. The reaction was then quenched by the addition of 50 mL of water. The resulting mixture was concentrated under vacuum. The resulting solution was diluted with 50 mL of H2O. The pH value of the aqueous solution was adjusted to 2 with aq. hydrogen chloride (5 N). The aqueous solution was washed with 3×20 mL of EA and adjusted to pH to 11 with sodium hydroxide. The resulting aqueous solution was extracted with 3×50 mL of ethyl acetate and the organic layers combined and concentrated under vacuum. This resulted in 5 g (50%) of 2-(2-bromophenyl)ethanamine as brown oil. Into a 500-mL 3-necked round-bottom flask, was placed with stiffing at 0° C The reaction was then quenched by the addition of 50 mL of water The resulting mixture was concentrated under vacuum The resulting solution was diluted with 50 mL of H2O The aqueous solution was washed with 3×20 mL of EA The resulting aqueous solution was extracted with 3×50 mL of ethyl acetate concentrated under vacuum This resulted in 5 g (50%) of 2-(2-bromophenyl)ethanamine as brown oil