dibutyl sulfate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,4-dibromothiophene (4.60 g, 20.90 mmol) in dry Et2O (50 mL) at -78° C. was dropwise added n-BuLi (2.5 M, 16.72 mL, 41.80 mmol) under Ar. After stirring for 15 min, a solution of freshly distilled di-n-butyl sulfate in dry Et2O (10 mL) was dropwise added through an addition funnel. The mixture was allowed to warm to room temperature and stirred overnight. 30 mL of 12 M NH4OH was added to the mixture. After stirring for 1 h, the mixture was partitioned between H2O and Et2O. The organic layer was separated and washed with H2O, brine and dried (MgSO4). Removal of the solvent under reduced pressure afforded the title compound as an oil (2.50 g, 60%). at -78° C. stirred overnight After stirring for 1 h the mixture was partitioned between H2O and Et2O The organic layer was separated washed with H2O, brine dried (MgSO4) Removal of the solvent under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,4-dibromothiophene (4.60 g, 20.90 mmol) in dry Et2O (50 mL) at -78° C. was dropwise added n-BuLi (2.5 M, 16.72 mL, 41.80 mmol) under Ar. After stirring for 15 min, a solution of freshly distilled di-n-butyl sulfate in dry Et2O (10 mL) was dropwise added through an addition funnel. The mixture was allowed to warm to room temperature and stirred overnight. 30 mL of 12 M NH4OH was added to the mixture. After stirring for 1 h, the mixture was partitioned between H2O and Et2O. The organic layer was separated and washed with H2O, brine and dried (MgSO4). Removal of the solvent under reduced pressure afforded the title compound as an oil (2.50 g, 60%). at -78° C. stirred overnight After stirring for 1 h the mixture was partitioned between H2O and Et2O The organic layer was separated washed with H2O, brine dried (MgSO4) Removal of the solvent under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,4-dibromothiophene (4.60 g, 20.90 mmol) in dry Et2O (50 mL) at -78° C. was dropwise added n-BuLi (2.5 M, 16.72 mL, 41.80 mmol) under Ar. After stirring for 15 min, a solution of freshly distilled di-n-butyl sulfate in dry Et2O (10 mL) was dropwise added through an addition funnel. The mixture was allowed to warm to room temperature and stirred overnight. 30 mL of 12 M NH4OH was added to the mixture. After stirring for 1 h, the mixture was partitioned between H2O and Et2O. The organic layer was separated and washed with H2O, brine and dried (MgSO4). Removal of the solvent under reduced pressure afforded the title compound as an oil (2.50 g, 60%). at -78° C. stirred overnight After stirring for 1 h the mixture was partitioned between H2O and Et2O The organic layer was separated washed with H2O, brine dried (MgSO4) Removal of the solvent under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Triethylphosphine (7.2 g, 99%, 0.06 mol) was added dropwise to a 125 mL flask containing 12.6 (99%, 0.06 mol) di-n-butylsulfate at 80° C. under nitrogen and with stirring over a period of 75 minutes. The liquid was stirred at 140° C. for an additional 3.5 hours. The liquid was cooled, moved to a rotary evaporator and dried at 125° C./5 mm Hg for 6 hours. The product (16.73 g, yield 85%) was a wax-like solid at room temperature (m.p. from DSC measurement: 40.0° C.). 1H-NMR (CDCl3, 300.13 MHz, δ): 3.98 (t, 2H, CH3CH2CH2—CH2—O—), 2.34 (m, 8H, 3×CH3—CH2P+ and CH3CH2CH2—CH2P+), 1.54 (m, 8H, CH3—CH2CH2—CH2O— and CH3—CH2CH2—CH2P+), 1.25 (m, 3×CH3—CH2P+), 0.91 (m, 6H, CH3CH2CH2—CH2O— and CH3CH2CH2—CH2P+). 31P-NMR (CDCl31 81.015 MHz, δ): 38.88 (s, P+). The liquid was stirred at 140° C. for an additional 3.5 hours The liquid was cooled moved to a rotary evaporator dried at 125° C./5 mm Hg for 6 hours

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,4-dibromothiophene (4.60 g, 20.90 mmol) in dry Et2O (50 mL) at -78° C. was dropwise added n-BuLi (2.5 M, 16.72 mL, 41.80 mmol) under Ar. After stirring for 15 min, a solution of freshly distilled di-n-butyl sulfate in dry Et2O (10 mL) was dropwise added through an addition funnel. The mixture was allowed to warm to room temperature and stirred overnight. 30 mL of 12 M NH4OH was added to the mixture. After stirring for 1 h, the mixture was partitioned between H2O and Et2O. The organic layer was separated and washed with H2O, brine and dried (MgSO4). Removal of the solvent under reduced pressure afforded the title compound as an oil (2.50 g, 60%). at -78° C. stirred overnight After stirring for 1 h the mixture was partitioned between H2O and Et2O The organic layer was separated washed with H2O, brine dried (MgSO4) Removal of the solvent under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3,4-dibromothiophene (4.60 g, 20.90 mmol) in dry Et2O (50 mL) at -78° C. was dropwise added n-BuLi (2.5 M, 16.72 mL, 41.80 mmol) under Ar. After stirring for 15 min, a solution of freshly distilled di-n-butyl sulfate in dry Et2O (10 mL) was dropwise added through an addition funnel. The mixture was allowed to warm to room temperature and stirred overnight. 30 mL of 12 M NH4OH was added to the mixture. After stirring for 1 h, the mixture was partitioned between H2O and Et2O. The organic layer was separated and washed with H2O, brine and dried (MgSO4). Removal of the solvent under reduced pressure afforded the title compound as an oil (2.50 g, 60%). at -78° C. stirred overnight After stirring for 1 h the mixture was partitioned between H2O and Et2O The organic layer was separated washed with H2O, brine dried (MgSO4) Removal of the solvent under reduced pressure