1,8-dibromooctane

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:

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

Procedure: Using the method described in Example 5(i), 1,8-dibromooctane (27.2 g, 0.1 mol) and ethylisobutyrate (10.44 g, 0.09 mol) were reacted in the presence of lithium diisopropylamide (67 ml, 0.1 mol) and hexamethylphosphoramide (22 g) to give the title compound (4.56 g) as an oil.

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

Procedure: in THF (30 mL) was added n-BuLi (1.6 M. 5.8 mmol). After 30 minutes 4-(triisopropylsilyloxy)benzaldehyde (1.5 g, 5.3 mmol) in THF (2 mL) was added into the reaction mixture. The reaction mixture was warmed to room temperature and quenched with aq. NH4Cl. The water phase was extracted with EtOAc and the combined extracts were washed with brine, dried over Na2SO4, and concentrated in vaccuo to provide the crude product. Purification by silica gel chromatography provide (4-chlorophenyl)(4-(triisopropylsilyloxy)phenyl)methanol (1.7 g, 4.2 mmol). (4-Chlorophenyl)(4-(triisopropylsilyloxy)phenyl)methanol (1.7 g, 4.2 mmol) was dissolved in THF (5 mL) and TBAF (1.0 M, 6.0 mmol) was added. After 15 minutes, the reaction mixture was quenched with MeOH (10 mL), concentrated, and the residue was purified by silica gel chromatography to afford4-((4-chlorophenyl)(hydroxy)methyl)phenol (963.1 mg, 4.1 mmol). This was subjected to alkylation with 1,8-dibromooctane (3.3 g, 12.3 mmol) and K2CO3 (1.7 g, 12.3 mmol) in DMF (45 mL). After 12h the reaction mixture was diluted with water (150 mL) and water phase was extracted with EtOAc (twice). The combined organic phase was washed with brine, dried over Na2SO4, and concentrated in vaccuo to give the crude product. Purification by silica gel chromatography provided (4-(8-bromooctyloxy)phenyl)(4-chlorophenyl)methanol (1.6 g, 3.7 mmol). the reaction mixture was quenched with MeOH (10 mL) concentrated was extracted with EtOAc (twice) The combined organic phase was washed with brine dried over Na2SO4 concentrated in vaccuo to give the crude product Purification by silica gel chromatography

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

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

Procedure: 4,5-Diphenyl-1,2,3-triazole was treated with 1,8-dibromooctane and potassium carbonate in butanone to give after chromatographic work up the title compound, m.p. 90°-91° C., Found: C, 64.0; H, 6.5; N, 10.1; Br, 19.8%; C22H26BrN3 requires: C, 64.1;H, 6.4; N, 10.2; Br, 19.4%.

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

Procedure: 4,5-Diphenyl-1,2,3-triazole was treated with 1,8-dibromooctane and potassium carbonate in butanone to give after chromatographic work up the title compound, m.p. 90°-91° C., Found: C, 64.0; H, 6.5; N, 10.1; Br, 19.8%; C22H26BrN3 requires: C, 64.1;H, 6.4; N, 10.2; Br, 19.4%.

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

Procedure: A mixture of 4,5-diphenyltriazole (11 g), 1,8-dibromooctane (67.6 g), and potassium carbonate (10.31 g) in dry butanone (300 ml) was heated at reflux temperature for 24 hours. The mixture was filtered and the solvent evaporated to give an oily residue. Distillation to remove 1,8-dibromooctane and column chromatography on silica gel eluted with a hexane:ethyl acetate gradient gave 2-(8-bromooctyl)-4,5-diphenyl-triazole (11.13 g, 54%) as an oil. NMR d (CDCl3) 1.2-1.5 (8H, m, 4×CH2), 1.84 (2H, m, CH2), 2.05 (2H, m, CH2), 3.37 (2H, t, Br--CH2), 4.47 (2H, t, N--CH2), 7.3-7.6 (10H, m, 2×Ph) ppm was heated at reflux temperature for 24 hours The mixture was filtered the solvent evaporated to give an oily residue Distillation to remove 1,8-dibromooctane and column chromatography on silica gel eluted with a hexane

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

Procedure: A mixture of 4,5-diphenyltriazole (11 g), 1,8-dibromooctane (67.6 g), and potassium carbonate (10.31 g) in dry butanone (300 ml) was heated at reflux temperature for 24 hours. The mixture was filtered and the solvent evaporated to give an oily residue. Distillation to remove 1,8-dibromooctane and column chromatography on silica gel eluted with a hexane:ethyl acetate gradient gave 2-(8-bromooctyl)-4,5-diphenyl-triazole (11.13 g, 54%) as an oil. NMR d (CDCl3) 1.2-1.5 (8H, m, 4×CH2), 1.84 (2H, m, CH2), 2.05 (2H, m, CH2), 3.37 (2H, t, Br--CH2), 4.47 (2H, t, N--CH2), 7.3-7.6 (10H, m, 2×Ph) ppm was heated at reflux temperature for 24 hours The mixture was filtered the solvent evaporated to give an oily residue Distillation to remove 1,8-dibromooctane and column chromatography on silica gel eluted with a hexane