methyl 2-(2-cyanophenoxy)acetate

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

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

Procedure: The methanol solution of methyl (2-cyanophenoxy)acetate (40 g, 0.209 mol) was added to the mixture of Raney Ni (80 g) in 500 mL of methanol. The reaction mixture was stirred at room temperature overnight under hydrogen atmosphere. Raney Ni was removed by filtration, and the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50) to give 23 g of product. MS obsd. (ESI+) [(M+H)+] 164. Raney Ni was removed by filtration the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50)

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

Procedure: The methanol solution of methyl (2-cyanophenoxy)acetate (40 g, 0.209 mol) was added to the mixture of Raney Ni (80 g) in 500 mL of methanol. The reaction mixture was stirred at room temperature overnight under hydrogen atmosphere. Raney Ni was removed by filtration, and the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50) to give 23 g of product. MS obsd. (ESI+) [(M+H)+] 164. Raney Ni was removed by filtration the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50)

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

Procedure: To the mixture of 2-hydroxybenzonitrile (40 g, 0.34 mol) and potassium carbonate (51.6 g, 0.374 mol) in 850 mL of acetone was added methyl bromoacetate (51.7 g, 0.34 mol) slowly at room temperature. After being stirred at room temperature overnight, the solid was filtered off. The filtrate was concentrated under reduced pressure and the residue was dissolved in ethyl acetate. The organic layer was washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give a residue which was recrystallized in methanol to give 40 g of product as a white solid. the solid was filtered off The filtrate was concentrated under reduced pressure the residue was dissolved in ethyl acetate The organic layer was washed with water brine, dried over sodium sulfate filtered concentrated under reduced pressure to give a residue which was recrystallized in methanol

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

Procedure: The methanol solution of methyl (2-cyanophenoxy)acetate (40 g, 0.209 mol) was added to the mixture of Raney Ni (80 g) in 500 mL of methanol. The reaction mixture was stirred at room temperature overnight under hydrogen atmosphere. Raney Ni was removed by filtration, and the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50) to give 23 g of product. MS obsd. (ESI+) [(M+H)+] 164. Raney Ni was removed by filtration the filtrated was concentrated under reduced pressure to give a residue which was purified by column chromatography on silica gel (methanol/dichloromethane, 1:50)

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

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl bromoacetate (1.95 mL, 20 mmol) is added dropwise to a solution of 2-cyanophenol (2.38 g, 20 mmol), and K2CO3 (2.78 g, 20.1 mmol) in acetone (100 mL) stirred under N2 at 25° C. After 24 h, the solid is filtered off and the filtrate is concentrated in vacuo and the residue is dried in a vacuum oven to give methyl 2-(2-cyanophenoxy)ethanoate (3.82 g, 100%) as a beige solid. 1H NMR (DMSO) δ7.76 (1H, dd, J=7.6, 1.7 Hz), 7.64 (1H, dt, Jd =1.6 Hz, Jt =8.0 Hz), 7.20~7.10 (2H, m), 5.04 (2H, brs), 3.70 (3H, s). the solid is filtered off the filtrate is concentrated in vacuo the residue is dried in a vacuum oven

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of methyl 2-(2-cyanophenoxy)ethanoate (3.82 g, 20 mmol) in DMSO (40 mL) is added dropwise to a suspension of NaH (0.84 g, 21 mmol) and DMSO (10 mL) stirred under N2 at 25° C. After 10 min the mixture is poured onto ice water and extracted with ether. The combined extracts are washed with water, saturated brine and dried (MgSO4). After removal of the solvent under reduced pressure, methyl 3-aminobenzo[b]furan-2-carboxylate (2.15 g, 56%) is obtained as a yellow solid. 1H NMR (DMSO) δ7.95 (1H, d, J=7.7 Hz), 7.48 (2H, d, J=3.4 Hz), 7.29-7.22 (1H, m), 6.40 (2H, brs), 3.80 (3H, s). After 10 min the mixture is poured onto ice water extracted with ether The combined extracts are washed with water, saturated brine dried (MgSO4) After removal of the solvent under reduced pressure

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl bromoacetate (1.95 mL, 20 mmol) is added dropwise to a solution of 2-cyanophenol (2.38 g, 20 mmol), and K2CO3 (2.78 g, 20.1 mmol) in acetone (100 mL) stirred under N2 at 25° C. After 24 h, the solid is filtered off and the filtrate is concentrated in vacuo and the residue is dried in a vacuum oven to give methyl 2-(2-cyanophenoxy)ethanoate (3.82 g, 100%) as a beige solid. 1H NMR (DMSO) δ7.76 (1H, dd, J=7.6, 1.7 Hz), 7.64 (1H, dt, Jd=1.6 Hz, Jt=8.0 Hz), 7.20˜7.10 (2H, m), 5.04 (2H, brs), 3.70 (3H, s). the solid is filtered off the filtrate is concentrated in vacuo the residue is dried in a vacuum oven

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

Procedure: To the mixture of 2-hydroxybenzonitrile (40 g, 0.34 mol) and potassium carbonate (51.6 g, 0.374 mol) in 850 mL of acetone was added methyl bromoacetate (51.7 g, 0.34 mol) slowly at room temperature. After being stirred at room temperature overnight, the solid was filtered off. The filtrate was concentrated under reduced pressure and the residue was dissolved in ethyl acetate. The organic layer was washed with water then brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give a residue which was recrystallized in methanol to give 40 g of product as a white solid. the solid was filtered off The filtrate was concentrated under reduced pressure the residue was dissolved in ethyl acetate The organic layer was washed with water brine, dried over sodium sulfate filtered concentrated under reduced pressure to give a residue which was recrystallized in methanol