1-bromo-4-(1-bromoethyl)benzene

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: The product from Example 44A (995 mg, 3.77 mmol) was reacted with 4-chloro-3-nitro-phenol (650 mg, 3.77 mmol) in 15 mL of DMF with K2CO3 (10.4 g, 3.77 mmol) at 80° C. for 3 h. Cooled to room temperature and diluted with water. Extracted with CH2Cl2, washed four times with water. Dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (1.24 g, 92%). Extracted with CH2Cl2 washed four times with water Dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: A solution of 1-(4-bromo-phenyl)-ethanol (4.21 g, 20.9 mmol) in 15 mL of CH2Cl2 was reacted with 15 mL of 1.0M PBr3 in CH2Cl2 at room temperature for 4 h. Quenched by pouring into ice and adjusted to pH 9 with 5% aqueous NaHCO3. Extracted with CH2Cl2 and dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (4.1 g, 75%). Quenched by pouring into ice Extracted with CH2Cl2 dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: A solution of 1-(4-bromo-phenyl)-ethanol (4.21 g, 20.9 mmol) in 15 mL of CH2Cl2 was reacted with 15 mL of 1.0M PBr3 in CH2Cl2 at room temperature for 4 h. Quenched by pouring into ice and adjusted to pH 9 with 5% aqueous NaHCO3. Extracted with CH2Cl2 and dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (4.1 g, 75%). Quenched by pouring into ice Extracted with CH2Cl2 dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: The product from Example 22A (995 mg, 3.77 mmol) was reacted with 4-chloro-3-nitro-phenol (650 mg, 3.77 mmol) in 15 mL of DMF with K2CO3 (10.4 g, 3.77 mmol) at 80° C. for 3 h. Cooled to room temperature and diluted with water. Extracted with CH2Cl2, washed four times with water. Dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (1.24 g, 92%). Extracted with CH2Cl2 washed four times with water Dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: A solution of 1-(4-bromo-phenyl)-ethanol (4.21 g, 20.9 mmol) in 15 mL of CH2Cl2 was reacted with 15 mL of 1.0M PBr3 in CH2Cl2 at room temperature for 4 h. Quenched by pouring into ice and adjusted to pH 9 with 5% aqueous NaHCO3. Extracted with CH2Cl2 and dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (4.1 g, 75%). Quenched by pouring into ice Extracted with CH2Cl2 dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: A solution of 1-(4-bromo-phenyl)-ethanol (4.21 g, 20.9 mmol) in 15 mL of CH2Cl2 was reacted with 15 mL of 1.0M PBr3 in CH2Cl2 at room temperature for 4 h. Quenched by pouring into ice and adjusted to pH 9 with 5% aqueous NaHCO3. Extracted with CH2Cl2 and dried over Na2SO4, filtered and concentrated under vacuum giving the title compound (4.1 g, 75%). Quenched by pouring into ice Extracted with CH2Cl2 dried over Na2SO4 filtered concentrated under vacuum

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

Procedure: To a 50 mL round-bottomed flask containing polystyrene resin (5 Scheme 18, 200 mg, 0.30 mequiv/g) in dry THF (15 mL) at −78° C. was added methylmagnesium bromide (10 equiv). The reaction slurry was stirred for 1 h at −78° C., then warmed slowly to room temperature and further stirred for 2 h. After cooling the flask to −20° C., saturated NH4Cl (0.5 mL) was added, and the mixture was stirred for 20 min at room temperature. The resin was filtered and washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure. To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL). After agitation for 20 min, the cleavage solution was removed, and the resin was rinsed with CH2Cl2 (5 mL). Concentration of the combined filtrates gave 4-bromo-α-methyl benzyl bromide (7 Scheme 18) as a colorless oil (12 mg, 75%); 1H NMR (300 MHz, CDCl3) δ 2.03 (d, J=6.97 Hz, 3 H), 5.17 (q, J=6.97 Hz, 1 H), 7.32 (d, J=8.49, 2 H), 7.49 (d, J=8.49, 2 H); 13C NMR (75 MHz, CDCl3) 27.0, 48.5, 122.4, 128.8 (2C), 132.1 (2C), 142.5. warmed slowly to room temperature further stirred for 2 h After cooling the flask to −20° C. the mixture was stirred for 20 min at room temperature The resin was filtered washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL) After agitation for 20 min the cleavage solution was removed the resin was rinsed with CH2Cl2 (5 mL)

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

Procedure: To a 50 mL round-bottomed flask containing polystyrene resin (5 Scheme 18, 200 mg, 0.30 mequiv/g) in dry THF (15 mL) at −78° C. was added methylmagnesium bromide (10 equiv). The reaction slurry was stirred for 1 h at −78° C., then warmed slowly to room temperature and further stirred for 2 h. After cooling the flask to −20° C., saturated NH4Cl (0.5 mL) was added, and the mixture was stirred for 20 min at room temperature. The resin was filtered and washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure. To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL). After agitation for 20 min, the cleavage solution was removed, and the resin was rinsed with CH2Cl2 (5 mL). Concentration of the combined filtrates gave 4-bromo-α-methyl benzyl bromide (7 Scheme 18) as a colorless oil (12 mg, 75%); 1H NMR (300 MHz, CDCl3) δ 2.03 (d, J=6.97 Hz, 3 H), 5.17 (q, J=6.97 Hz, 1 H), 7.32 (d, J=8.49, 2 H), 7.49 (d, J=8.49, 2 H); 13C NMR (75 MHz, CDCl3) 27.0, 48.5, 122.4, 128.8 (2C), 132.1 (2C), 142.5. warmed slowly to room temperature further stirred for 2 h After cooling the flask to −20° C. the mixture was stirred for 20 min at room temperature The resin was filtered washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL) After agitation for 20 min the cleavage solution was removed the resin was rinsed with CH2Cl2 (5 mL)

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

Procedure: To a 50 mL round-bottomed flask containing polystyrene resin (5 Scheme 18, 200 mg, 0.30 mequiv/g) in dry THF (15 mL) at −78° C. was added methylmagnesium bromide (10 equiv). The reaction slurry was stirred for 1 h at −78° C., then warmed slowly to room temperature and further stirred for 2 h. After cooling the flask to −20° C., saturated NH4Cl (0.5 mL) was added, and the mixture was stirred for 20 min at room temperature. The resin was filtered and washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure. To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL). After agitation for 20 min, the cleavage solution was removed, and the resin was rinsed with CH2Cl2 (5 mL). Concentration of the combined filtrates gave 4-bromo-α-methyl benzyl bromide (7 Scheme 18) as a colorless oil (12 mg, 75%); 1H NMR (300 MHz, CDCl3) δ 2.03 (d, J=6.97 Hz, 3 H), 5.17 (q, J=6.97 Hz, 1 H), 7.32 (d, J=8.49, 2 H), 7.49 (d, J=8.49, 2 H); 13C NMR (75 MHz, CDCl3) 27.0, 48.5, 122.4, 128.8 (2C), 132.1 (2C), 142.5. warmed slowly to room temperature further stirred for 2 h After cooling the flask to −20° C. the mixture was stirred for 20 min at room temperature The resin was filtered washed with 1:1 THF/water (twice), water (twice), methanol (twice), CH2Cl2 (twice), then dried under reduced pressure To a slurry of resin in CH2Cl2 (8 mL) was added Br2 (100 μL) After agitation for 20 min the cleavage solution was removed the resin was rinsed with CH2Cl2 (5 mL)