7-METHOXY-3(2H)-BENZOFURANONE

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

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

Procedure: The solution of 7-methoxy-1-benzofuran-3(2H)-one (reference) (7.5 g, 0.046 mol), cyanoacetic acid (19.55 g, 0.23 mol) and ammonium acetate (7.08 g, 0.092 mol) in xylene was refluxed for 16-18 h. using dean stark apparatus. Xylene was removed under diminished pressure. Brown black residue was taken in ethyl acetate, washed with water and concentrated. On purification on silica gel it yielded (7-methoxy-1-benzofuran-3-yl)acetonitrile (30%). Xylene was removed under diminished pressure washed with water concentrated On purification on silica gel it

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trifluoromethanesulfonic anhydride (4.6 g, 16.3 mmol) was added dropwise to a solution of 7-methoxybenzofuran-3(2H)-one (1.8 g, 10.9 mmol), triethylamine (2.2 g, 21.8 mmol), and dichloromethane (40 mL) at −20° C. The resulting mixture was stirred at −20° C. for 2 h. The reaction mixture was neutralized with saturated aqueous NaHCO3 (22 mL). The organic layer was separated, washed with water (40 mL) and brine (40 mL), dried over Na2SO4, and concentrated in vacuo. The residue was purified on a silica gel column using petroleum ether to afford the title compound as yellow oil (2.3 g, yield 71%). 1H NMR (DMSO-d6, 400 MHz): δ 8.67 (s, 1H), 7.36 (t, 1H), 7.21 (d, 1H), 7.20 (d, 1H), 3.96 (s, 3H). The organic layer was separated washed with water (40 mL) and brine (40 mL) dried over Na2SO4 concentrated in vacuo The residue was purified on a silica gel column

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

Procedure: The solution of 7-methoxy-1-benzofuran-3(2H)-one (reference) (7.5 g, 0.046 mol), cyanoacetic acid (19.55 g, 0.23 mol) and ammonium acetate (7.08 g, 0.092 mol) in xylene was refluxed for 16-18 h. using dean stark apparatus. Xylene was removed under diminished pressure. Brown black residue was taken in ethyl acetate, washed with water and concentrated. On purification on silica gel it yielded (7-methoxy-1-benzofuran-3-yl)acetonitrile (30%). Xylene was removed under diminished pressure washed with water concentrated On purification on silica gel it

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

Procedure: The solution of 7-methoxy-1-benzofuran-3(2H)-one (reference) (7.5 g, 0.046 mol), cyanoacetic acid (19.55 g, 0.23 mol) and ammonium acetate (7.08 g, 0.092 mol) in xylene was refluxed for 16-18 h. using dean stark apparatus. Xylene was removed under diminished pressure. Brown black residue was taken in ethyl acetate, washed with water and concentrated. On purification on silica gel it yielded (7-methoxy-1-benzofuran-3-yl)acetonitrile (30%). Xylene was removed under diminished pressure washed with water concentrated On purification on silica gel it

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

Procedure: A mixture of 14.16 g of 7-methoxy-3-benzofuranone, 39.4 g of cyanomethylenetriphenylphosphorane and 70 ml of p-xylene was heated at reflux under nitrogen for 16 hours. The solvent was removed, the solid washed repeatedly with ether and the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron). Crystallization of the sublimate from 20 ml of isopropyl alcohol gave 11.06 g (69% yield) of 7-methoxy-3-benzofuranacetonitrile. Nmr spectrum (in CDCl3): τ2.4 (t, J=1-2 Hz, 1); 2.8-3.3 (m, 3); 6.0 (s, 3) and 6.3 (d, J=1-2 Hz, 2). was heated at reflux under nitrogen for 16 hours The solvent was removed the solid washed repeatedly with ether the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron) Crystallization of the sublimate from 20 ml of isopropyl alcohol

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

Procedure: A mixture of 14.16 g of 7-methoxy-3-benzofuranone, 39.4 g of cyanomethylenetriphenylphosphorane and 70 ml of p-xylene was heated at reflux under nitrogen for 16 hours. The solvent was removed, the solid washed repeatedly with ether and the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron). Crystallization of the sublimate from 20 ml of isopropyl alcohol gave 11.06 g (69% yield) of 7-methoxy-3-benzofuranacetonitrile. Nmr spectrum (in CDCl3): τ2.4 (t, J=1-2 Hz, 1); 2.8-3.3 (m, 3); 6.0 (s, 3) and 6.3 (d, J=1-2 Hz, 2). was heated at reflux under nitrogen for 16 hours The solvent was removed the solid washed repeatedly with ether the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron) Crystallization of the sublimate from 20 ml of isopropyl alcohol

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

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

Procedure: To a cold (ice water) solution of 7-methoxy-3-(2H)-benzofuranone (846 mg; 5.0 mmol) in methanol (5 mL) is added sodium borohydride (179 mg; 5.0 mmol) is stirred for 15 minutes. Water (5 mL) is added to the solution and stirred 15 minutes. Saturated ammonium chloride (20 mL) is added and the solution is extracted with ethyl acetate. The organics are separated and dried over magnesium sulfate. The solvent is removed to give 831 milligrams of 7-methoxy-2,3-dihydrobenzofuran-3-ol. stirred 15 minutes the solution is extracted with ethyl acetate The organics are separated dried over magnesium sulfate The solvent is removed

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

Procedure: A mixture of 7-methoxy-benzofuran-3 (2H)-one (1.64 g, 10 mmol) and 1-triphenylphosphoranylidene-2-propanone (4.77 g, 15 mmol) was refluxed in toluene (100 ml) for 48 hrs. At the end, the reaction mixture was concentrated and loaded over a silica-gel column. The column was eluted with hexane (500 ml) and later with 25% ethyl acetate. The product, 1-(7-methoxy-1-benzofuran-3-yl)acetone, was obtained as a red oil. Yield: 1.4 g (68%); 205 (M+H). At the end, the reaction mixture was concentrated The column was eluted with hexane (500 ml) and later with 25% ethyl acetate

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

Procedure: A mixture of 7-methoxy-benzofuran-3 (2H)-one (1.64 g, 10 mmol) and (carboxymethylene)triphenylphosphorane (5.22 g, 15 mmol) was refluxed in toluene (100 ml) for 48 hrs. At the end, the reaction mixture was concentrated and loaded over silica-gel column. The column was eluted with hexane (500 ml) and later with 25% ethyl acetate. The product, ethyl(7-methoxy-1-benzofuran-3-yl)acetate was obtained as a white oil. Yield: 1.9 g (81%); 235 (M+H). At the end, the reaction mixture was concentrated The column was eluted with hexane (500 ml) and later with 25% ethyl acetate

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

Procedure: A mixture of 14.16 g of 7-methoxy-3-benzofuranone, 39.4 g of cyanomethylenetriphenylphosphorane and 70 ml of p-xylene was heated at reflux under nitrogen for 16 hours. The solvent was removed, the solid washed repeatedly with ether and the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron). Crystallization of the sublimate from 20 ml of isopropyl alcohol gave 11.06 g (69% yield) of 7-methoxy-3-benzofuranacetonitrile. Nmr spectrum (in CDCl3): τ2.4 (t, J=1-2 Hz, 1); 2.8-3.3 (m, 3); 6.0 (s, 3) and 6.3 (d, J=1-2 Hz, 2). was heated at reflux under nitrogen for 16 hours The solvent was removed the solid washed repeatedly with ether the product obtained on removal of the solvent from the ether washings sublimed (145° bath, 1 micron) Crystallization of the sublimate from 20 ml of isopropyl alcohol