1-bromo-4-propylsulfanylbenzene

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

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

Procedure: Dissolve 4-bromo-benzenethiol (2.0 g, 10.6 mmol) in dry dimethylformamide (50 mL) and cool to 0° C. under nitrogen. Add sodium hydride (305 mg, 12.7 mmol) in portions. After the vigorous gas evolution stops, add 1-bromo-propane (1.4 mL, 15.9 mmol) and stir the reaction mixture overnight at room temperature. Slowly pour the reaction into water (400 mL) and extract with diethyl ether (2×150 mL). Wash the combined organic layers with water (100 mL). Dry the organic layer with sodium sulfate, filter and concentrate in vacuo to yield 2.7 g of 1-bromo-4-propylsulfanyl-benzene (quantitative yield). Slowly pour extract with diethyl ether (2×150 mL) Wash the combined organic layers with water (100 mL) Dry the organic layer with sodium sulfate filter concentrate in vacuo

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

Procedure: Dissolve 4-bromo-benzenethiol (2.0 g, 10.6 mmol) in dry dimethylformamide (50 mL) and cool to 0° C. under nitrogen. Add sodium hydride (305 mg, 12.7 mmol) in portions. After the vigorous gas evolution stops, add 1-bromo-propane (1.4 mL, 15.9 mmol) and stir the reaction mixture overnight at room temperature. Slowly pour the reaction into water (400 mL) and extract with diethyl ether (2×150 mL). Wash the combined organic layers with water (100 mL). Dry the organic layer with sodium sulfate, filter and concentrate in vacuo to yield 2.7 g of 1-bromo-4-propylsulfanyl-benzene (quantitative yield). Slowly pour extract with diethyl ether (2×150 mL) Wash the combined organic layers with water (100 mL) Dry the organic layer with sodium sulfate filter concentrate in vacuo

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

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

Procedure: To a stirred solution of 1-bromo-4-(propylthio)benzene (500 mg, 2.16 mmol) in THF (10 ml) at −78° C. was added n-butyllithium (2.5 M in hexanes, 0.91 ml, 2.27 mmol). The resulting yellow solution was stirred at −78° C. for 15 minutes then pivaldehyde (0.29 ml, 2.59 mmol) was added. The mixture was allowed to warm to room temperature, during which time the solution turned colourless. The mixture was partitioned between ethyl acetate (60 ml) and water (30 ml). The organic phase was separated, washed with brine (30 ml), dried over MgSO4 filtered and evaporated to give a colourless oil. The crude product was chromatographed on silica eluting with 5% ethyl acetate in hexanes to give the title product as a pale yellow oil (468 mg). 1H NMR δ (CDCl3) 7.28-7.20 (4H, m), 4.36 (1H, s), 2.89 (2H, t, J=7.3 Hz), 1.84 (1H, s), 1.71-1.63 (2H, m), 1.02 (3H, t, J=7.3 Hz), 0.91 (9H, s). to warm to room temperature, during which time the solution The mixture was partitioned between ethyl acetate (60 ml) and water (30 ml) The organic phase was separated washed with brine (30 ml) dried over MgSO4 filtered evaporated to give a colourless oil The crude product was chromatographed on silica eluting with 5% ethyl acetate in hexanes

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

Procedure: Add oxone (potassium mono persulfate, 15.03 g, 24.4 mmol) in one portion to a cold (0° C.) stirred solution of 1-bromo-4-propylsulfanyl-benzene (1.881 g, 8.14 mmol) in THF (20 mL), methanol (10 mL), and water (10 mL) and slowly warm to room temperature overnight. Remove the solvents under reduced pressure and add dichloromethane and water to the residue. Separate the layers, extract the aqueous layer twice with dichloromethane, wash the organic layer with saturated aqueous sodium bicarbonate, dry over anhydrous magnesium sulfate, and concentrate under reduced pressure. Purify the residue by flash chromatography (SiO2, elute 0% to 30% EtOAc/hexanes) to yield 1.96 g of the title compound as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J=9.2 Hz, 2H), 7.74 (d, J=8.8 Hz, 2H), 3.06-3.11 (m, 2H), 1.72-1.83 (m, 2H), 1.04 (dd, J=7.2, 7.2 Hz, 3H). Remove the solvents under reduced pressure add dichloromethane and water to the residue Separate the layers extract the aqueous layer twice with dichloromethane wash the organic layer with saturated aqueous sodium bicarbonate dry over anhydrous magnesium sulfate concentrate under reduced pressure Purify the residue by flash chromatography (SiO2, elute 0% to 30% EtOAc/hexanes)

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

Procedure: Dissolve 4-bromo-benzenethiol (2.0 g, 10.6 mmol) in dry dimethylformamide (50 mL) and cool to 0° C. under nitrogen. Add sodium hydride (305 mg, 12.7 mmol) in portions. After the vigorous gas evolution stops, add 1-bromo-propane (1.4 mL, 15.9 mmol) and stir the reaction mixture overnight at room temperature. Slowly pour the reaction into water (400 mL) and extract with diethyl ether (2×150 mL). Wash the combined organic layers with water (100 mL). Dry the organic layer with sodium sulfate, filter and concentrate in vacuo to yield 2.7 g of 1-bromo-4-propylsulfanyl-benzene (quantitative yield). Slowly pour extract with diethyl ether (2×150 mL) Wash the combined organic layers with water (100 mL) Dry the organic layer with sodium sulfate filter concentrate in vacuo

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

Procedure: Dissolve 4-bromo-benzenethiol (2.0 g, 10.6 mmol) in dry dimethylformamide (50 mL) and cool to 0° C. under nitrogen. Add sodium hydride (305 mg, 12.7 mmol) in portions. After the vigorous gas evolution stops, add 1-bromo-propane (1.4 mL, 15.9 mmol) and stir the reaction mixture overnight at room temperature. Slowly pour the reaction into water (400 mL) and extract with diethyl ether (2×150 mL). Wash the combined organic layers with water (100 mL). Dry the organic layer with sodium sulfate, filter and concentrate in vacuo to yield 2.7 g of 1-bromo-4-propylsulfanyl-benzene (quantitative yield). Slowly pour extract with diethyl ether (2×150 mL) Wash the combined organic layers with water (100 mL) Dry the organic layer with sodium sulfate filter concentrate in vacuo