methyl 3,5-bis(bromomethyl)benzoate

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

実験手順: Methyl 3,5-bis(bromomethyl)-benzoate (500 mg, 1.6 mmol) and di-(2-picolyl)-amine (800 mg, 725 μL, 4 mmol) were dissolved in ACN followed by the addition of dry K2CO3 (1.1 g, 7.9 mmol). The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube. The reaction mixture was filtered and filtrate was evaporated under reduced pressure. Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt was used to elute impurities and then MeOH/AcOEt=1:9 (v/v)) affording a pure product as a yellow oil. Yield: 850 mg (95%). 1H NMR (500 MHz, CDCl33) δ 8.51 (m, 4H), 7.94 (d, J=1.5 Hz, 2H), 7.70 (s, 1H), 7.61 (m, 8H), 7.12 (m, 4H), 3.92 (s, 3H), 3.81 (s, 8H), 3.73 (s, 4H). 13C NMR (101 MHz, CDCl3) δ 197.9, 167.1, 159.5, 148.9, 139.7, 136.2, 133.8, 130.2, 128.7, 122.8, 121.9, 60.1, 58.2, 52.0. MS (ESI, m/z): calculated: 558.7 observed: 559.5 [M+H]+. The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube The reaction mixture was filtered filtrate was evaporated under reduced pressure Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt to elute impurities

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

実験手順: Methyl 3,5-bis(bromomethyl)-benzoate (500 mg, 1.6 mmol) and di-(2-picolyl)-amine (800 mg, 725 μL, 4 mmol) were dissolved in ACN followed by the addition of dry K2CO3 (1.1 g, 7.9 mmol). The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube. The reaction mixture was filtered and filtrate was evaporated under reduced pressure. Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt was used to elute impurities and then MeOH/AcOEt=1:9 (v/v)) affording a pure product as a yellow oil. Yield: 850 mg (95%). 1H NMR (500 MHz, CDCl33) δ 8.51 (m, 4H), 7.94 (d, J=1.5 Hz, 2H), 7.70 (s, 1H), 7.61 (m, 8H), 7.12 (m, 4H), 3.92 (s, 3H), 3.81 (s, 8H), 3.73 (s, 4H). 13C NMR (101 MHz, CDCl3) δ 197.9, 167.1, 159.5, 148.9, 139.7, 136.2, 133.8, 130.2, 128.7, 122.8, 121.9, 60.1, 58.2, 52.0. MS (ESI, m/z): calculated: 558.7 observed: 559.5 [M+H]+. The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube The reaction mixture was filtered filtrate was evaporated under reduced pressure Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt to elute impurities

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

実験手順: Methyl 3,5-bis(bromomethyl)-benzoate (500 mg, 1.6 mmol) and di-(2-picolyl)-amine (800 mg, 725 μL, 4 mmol) were dissolved in ACN followed by the addition of dry K2CO3 (1.1 g, 7.9 mmol). The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube. The reaction mixture was filtered and filtrate was evaporated under reduced pressure. Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt was used to elute impurities and then MeOH/AcOEt=1:9 (v/v)) affording a pure product as a yellow oil. Yield: 850 mg (95%). 1H NMR (500 MHz, CDCl33) δ 8.51 (m, 4H), 7.94 (d, J=1.5 Hz, 2H), 7.70 (s, 1H), 7.61 (m, 8H), 7.12 (m, 4H), 3.92 (s, 3H), 3.81 (s, 8H), 3.73 (s, 4H). 13C NMR (101 MHz, CDCl3) δ 197.9, 167.1, 159.5, 148.9, 139.7, 136.2, 133.8, 130.2, 128.7, 122.8, 121.9, 60.1, 58.2, 52.0. MS (ESI, m/z): calculated: 558.7 observed: 559.5 [M+H]+. The reaction mixture was refluxed overnight under reflux condenser equipped with a CaCl2 tube The reaction mixture was filtered filtrate was evaporated under reduced pressure Yellow residue was purified by flash chromatography (Al2O3 neutral, firstly AcOEt to elute impurities

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of sodiumhydride (3.6 g, 90mmol) and N,N-dimethylformamide (150 ml) was cooled to 0° C. and treated with solid di-tert-butyliminodicarboxylate (17.4 g, 76.0 mmol) with vigorous stirring. The mixture was stirred at 0° C. for 15 minutes, the ice bath was removed and a solution of methyl 3,5-bis(bromomethyl)-benzoate (23.6 g, 73.2 mmol) in N,N-dimethylform was added dropwise over 30 minutes. After 12 hours the mixture was poured into 100 ml 1/4 saturated aqueous ammonium chloride and extracted with the three 100 ml portion of hexanes. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure and chromatographed using a gradient of 10-20% ethyl acetate/hexanes to yield the product (22.0 g, 66% yield). TLC (20% ethyl acetate/hexanes): Rf =0.55 (UV active, CAM stain) the ice bath was removed extracted with the three 100 ml portion of hexanes The organic layer was dried over magnesium sulfate concentrated under reduced pressure chromatographed

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of sodium hydride (3.6 g, 90 mmol) and N,N-dimethylformamide (150 ml) was cooled to 0° C. and treated with solid di-tert-butyliminodicarboxylate (17.4 g, 76.0 mmol) with vigorous stirring. The mixture was stirred at 0° C. for 15 minutes, the ice bath was removed and a solution of methyl-3,5-bis(bromomethyl)-benzoate (23.6 g, 73.2 mmol) in N,N-dimethylformamide was added dropwise over 30 minutes. After 12 hours the mixture was poured into 100 ml 1/4 saturated aqueous ammonium chloride and extracted with the three 100 ml portion of hexanes. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure and chromatographed using a gradient of 10-20% ethyl acetate/hexanes to yield the product (22.0 g, 66% yield). TLC (20% ethyl acetate/hexanes): Rf =0.55 (UV active, CAM stain) the ice bath was removed extracted with the three 100 ml portion of hexanes The organic layer was dried over magnesium sulfate concentrated under reduced pressure chromatographed

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of sodium hydride (3.6 g, 90 mmol) and N,N-dimethylformamide (150 ml) was cooled to 0° C. and treated with solid di-tert-butyliminodicarboxylate (17.4 g, 76.0 mmol) with vigorous stirring. The mixture was stirred at 0° C. for 15 minutes, the ice bath was removed and a solution of methyl-3,5-bis(bromomethyl)-benzoate (23.6 g, 73.2 mmol) in N,N-dimethylformamide was added dropwise over 30 minutes. After 12 hours the mixture was poured into 100 ml 1/4 saturated aqueous ammonium chloride and extracted with the three 100 ml portion of hexanes. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure and chromatographed using a gradient of 10-20% ethyl acetate/hexanes to yield the product (22.0 g, 66% yield). TLC (20% ethyl acetate/hexanes): Rf =0.55 (UV active, CAM stain) the ice bath was removed extracted with the three 100 ml portion of hexanes The organic layer was dried over magnesium sulfate concentrated under reduced pressure chromatographed