ethyl 2-[3-(hydroxymethyl)phenoxy]acetate

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

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

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

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

Procedure: To a solution of 3-hydroxymethyl-1-ethoxycarbonylmethoxybenzene (1 g) in dichloromethane (10 ml) was added BBr3 (0.45 ml). After 1 hour, the solvent was evaporated in vacuo and the residue was dissolved in ethyl acetate. The organic layer was washed with NaHCO3 and brine. The dried solvent was evaporated in vacuo to give 3-bromomethyl-1-ethoxycarbonylmethoxybenzene (0.76 g). the solvent was evaporated in vacuo the residue was dissolved in ethyl acetate The organic layer was washed with NaHCO3 and brine The dried solvent was evaporated in vacuo

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

Procedure: To a solution of ethyl 2-(3-(hydroxymethyl)phenoxy)acetate (2.00 g) and triethylamine (1.44 g) in THF (10 mL) was added methanesulfonyl chloride (1.31 g) at 0° C., and the mixture was stirred for 1 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (2.80 g) as a colorless oil. the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous magnesium sulfate The solvent was evaporated under reduced pressure the residue was purified by silica gel column chromatography (ethyl acetate/hexane)

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

Procedure: A solution containing ethyl 3-(hydroxymethyl)phenoxyacetate (2.6 g.) and carbon tetrabromide (8.3 g.) in DMF (30 ml.) was treated with a solution of triphenylphosphine (6.55 g.) in DMF (20 ml.) with stirring. The temperature was maintained below 15° C. during the addition using an ice bath. After 1 hour the mixture was poured into ice-water (300 ml.) and the aqueous mixture was extracted with ether (3×100 ml.). The combined extracts were washed with water (3×100 ml.) and saturated brine (100 ml.), dried (MgSO4) and concentrated. The resultant oil was purified by flash column chromatography, eluting with petrol (60°-80° )/ether (80:20 v/v) to give ethyl 3 (bromomethyl)phenoxyacetate (2.4 g.) as a colourless oil, NMR: 1.3 (3H,t), 4.25 (2H,q), 4.4 (2H,s), 4.6 (2H,s) and 6.7-7.4 (4H,m)ppm. The temperature was maintained below 15° C. during the addition the aqueous mixture was extracted with ether (3×100 ml.) The combined extracts were washed with water (3×100 ml.) and saturated brine (100 ml.) dried (MgSO4) concentrated The resultant oil was purified by flash column chromatography eluting with petrol (60°-80° )/ether (80:20 v/v)

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

Procedure: A solution of 3-(hydroxymethyl)phenoxyacetic acid (3.18 g.) in ethanol (30 ml.) was treated with concentrated sulphuric acid (10 drops) and allowed to stand for 3 days. Chloroform (100 ml.) and water (50 ml.) were then added. The organic phase was separated, washed sequentially with saturated aqueous sodium hydrogen carbonate solution (2×50 ml.), water (50 ml.) and saturated brine (50 ml.) and then dried (MgSO4) The dried solution was evaporated and the residue purified by flash column chromatography, eluting with petrol (40°-60° )/ ethyl acetate (60:40 v/v) to give ethyl 3-(hydroxymethyl)phenoxyacetate (2.6 g.) as a colourless oil, NMR: 1.25 (3H,t), 2.8 (1H,br s), 4.25 (2H,q), 4.6 (4H,s) and 6.6-7.4 (4H,m)ppm. The organic phase was separated washed sequentially with saturated aqueous sodium hydrogen carbonate solution (2×50 ml.), water (50 ml.) and saturated brine (50 ml.) dried (MgSO4) The dried solution was evaporated the residue purified by flash column chromatography eluting with petrol (40°-60° )/ ethyl acetate (60:40 v/v)

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

Procedure: A solution of 3-(hydroxymethyl)phenoxyacetic acid (3.18 g.) in ethanol (30 ml.) was treated with concentrated sulphuric acid (10 drops) and allowed to stand for 3 days. Chloroform (100 ml.) and water (50 ml.) were then added. The organic phase was separated, washed sequentially with saturated aqueous sodium hydrogen carbonate solution (2×50 ml.), water (50 ml.) and saturated brine (50 ml.) and then dried (MgSO4) The dried solution was evaporated and the residue purified by flash column chromatography, eluting with petrol (40°-60° )/ ethyl acetate (60:40 v/v) to give ethyl 3-(hydroxymethyl)phenoxyacetate (2.6 g.) as a colourless oil, NMR: 1.25 (3H,t), 2.8 (1H,br s), 4.25 (2H,q), 4.6 (4H,s) and 6.6-7.4 (4H,m)ppm. The organic phase was separated washed sequentially with saturated aqueous sodium hydrogen carbonate solution (2×50 ml.), water (50 ml.) and saturated brine (50 ml.) dried (MgSO4) The dried solution was evaporated the residue purified by flash column chromatography eluting with petrol (40°-60° )/ ethyl acetate (60:40 v/v)

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

Procedure: To a solution of 3-hydroxymethyl-1-ethoxycarbonylmethoxybenzene (1 g) in dichloromethane (10 ml) was added BBr3 (0.45 ml). After 1 hour, the solvent was evaporated in vacuo and the residue was dissolved in ethyl acetate. The organic layer was washed with NaHCO3 and brine. The dried solvent was evaporated in vacuo to give 3-bromomethyl-1-ethoxycarbonylmethoxybenzene (0.76 g). the solvent was evaporated in vacuo the residue was dissolved in ethyl acetate The organic layer was washed with NaHCO3 and brine The dried solvent was evaporated in vacuo

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

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

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

Procedure: To a solution of ethyl 2-(3-(hydroxymethyl)phenoxy)acetate (2.00 g) and triethylamine (1.44 g) in THF (10 mL) was added methanesulfonyl chloride (1.31 g) at 0° C., and the mixture was stirred for 1 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (2.80 g) as a colorless oil. the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous magnesium sulfate The solvent was evaporated under reduced pressure the residue was purified by silica gel column chromatography (ethyl acetate/hexane)