ethyl 2-hydroxy-2-(4-hydroxyphenyl)acetate

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

Procedure: 15.3 g of chromium trioxide is added dropwise to a solution of 15 g of ethyl 4-hydroxymandelate in 240 ml of acetic acid. The mixture is stirred at room temperature for 2 hours, poured into 1 l of ethyl acetate and extracted with saturated aqueous Na2CO3 solution. The aqueous phases are extracted with methylene chloride. The organic phases are washed with saturated aqueous Na2CO3 solution, followed by washing with water. The organic phases are dried over sodium sulfate. Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar)) give 4.04 g (27 wt %) ethyl 4-hydroxybenzoylformate as a yellow solid. extracted with saturated aqueous Na2CO3 solution The aqueous phases are extracted with methylene chloride The organic phases are washed with saturated aqueous Na2CO3 solution by washing with water The organic phases are dried over sodium sulfate Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar))

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

Procedure: 15.3 g of chromium trioxide is added dropwise to a solution of 15 g of ethyl 4-hydroxymandelate in 240 ml of acetic acid. The mixture is stirred at room temperature for 2 hours, poured into 1 l of ethyl acetate and extracted with saturated aqueous Na2CO3 solution. The aqueous phases are extracted with methylene chloride. The organic phases are washed with saturated aqueous Na2CO3 solution, followed by washing with water. The organic phases are dried over sodium sulfate. Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar)) give 4.04 g (27 wt %) ethyl 4-hydroxybenzoylformate as a yellow solid. extracted with saturated aqueous Na2CO3 solution The aqueous phases are extracted with methylene chloride The organic phases are washed with saturated aqueous Na2CO3 solution by washing with water The organic phases are dried over sodium sulfate Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar))

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5 g of 4-hydroxymandelic acid and 1.28 g of p-toluenesulfonic acid in 200 ml of ethanol is heated at 50° C. for 4 hours. The mixture is poured into saturated aqueous NaHCO3 solution, and a white precipitate is formed. The mixture is diluted with water until the precipitate disintegrates, and then is extracted with diethyl ether. The organic phases are dried over sodium sulfate. Filtration and evaporation of the solvent give ethyl 4-hydroxymandelate (4.2 g, 82%) as a pale yellowish solid. a white precipitate is formed is extracted with diethyl ether The organic phases are dried over sodium sulfate Filtration and evaporation of the solvent

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

Procedure: A solution of ethyl 4-hydroxymandelate (19.6 g, 0.1 mol), 1,3-dibromopropane (60.75 g, 0.3 mol) and cesium carbonate (35.75 g, 0.11 mol) in dry DMF (200 mL) was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl. The organic layer was washed twice with water, once with brine and then dried over sodium sulfate. The organic layer was then filtered and the solvent remove in vacuo. The resulting oil was chromatographed on silica gel, using a gradient of 100% hexane to methylene chloride/hexane (2:1) to yield the titled compound. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl The organic layer was washed twice with water, once with brine dried over sodium sulfate The organic layer was then filtered the solvent remove in vacuo The resulting oil was chromatographed on silica gel

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

Procedure: A solution of ethyl 4-hydroxymandelate (19.6 g, 0.1 mol), 1,3-dibromopropane (60.75 g, 0.3 mol) and cesium carbonate (35.75 g, 0.11 mol) in dry DMF (200 mL) was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl. The organic layer was washed twice with water, once with brine and then dried over sodium sulfate. The organic layer was then filtered and the solvent remove in vacuo. The resulting oil was chromatographed on silica gel, using a gradient of 100% hexane to methylene chloride/hexane (2:1) to yield the titled compound. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl The organic layer was washed twice with water, once with brine dried over sodium sulfate The organic layer was then filtered the solvent remove in vacuo The resulting oil was chromatographed on silica gel

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

Procedure: Methanesulfonyl chloride (0.395 ml, 5.10 mmol) is added dropwise at 0° C. to ethyl 4-hydroxymandelate (0.500 g, 2.55 mmol) and triethylamine (0.889 ml, 6.38 mmol) in DMF (5 ml) and the mixture is allowed to warm to room temperature overnight. The reaction mixture is diluted with water and extracted with ethyl acetate. The extract is washed with brine, dried (MgSO4), and evaporated to give oily residue which is purified by flash column chromatography (30% EtOAc/Hexane) (0.75 g, 82%). MS (m/z): [M+H]+=353. extracted with ethyl acetate The extract is washed with brine dried (MgSO4) evaporated to give oily residue which is purified by flash column chromatography (30% EtOAc/Hexane) (0.75 g, 82%)

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

Procedure: Methanesulfonyl chloride (0.395 ml, 5.10 mmol) is added dropwise at 0° C. to ethyl 4-hydroxymandelate (0.500 g, 2.55 mmol) and triethylamine (0.889 ml, 6.38 mmol) in DMF (5 ml) and the mixture is allowed to warm to room temperature overnight. The reaction mixture is diluted with water and extracted with ethyl acetate. The extract is washed with brine, dried (MgSO4), and evaporated to give oily residue which is purified by flash column chromatography (30% EtOAc/Hexane) (0.75 g, 82%). MS (m/z): [M+H]+=353. extracted with ethyl acetate The extract is washed with brine dried (MgSO4) evaporated to give oily residue which is purified by flash column chromatography (30% EtOAc/Hexane) (0.75 g, 82%)

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

Procedure: A solution of ethyl 4-hydroxymandelate (19.6 g, 0.1 mol), 1,3-dibromopropane (60.75 g, 0.3 mol) and cesium carbonate (35.75 g, 0.11 mol) in dry DMF (200 mL) was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl. The organic layer was washed twice with water, once with brine and then dried over sodium sulfate. The organic layer was then filtered and the solvent remove in vacuo. The resulting oil was chromatographed on silica gel, using a gradient of 100% hexane to methylene chloride/hexane (2:1) to yield the titled compound. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl The organic layer was washed twice with water, once with brine dried over sodium sulfate The organic layer was then filtered the solvent remove in vacuo The resulting oil was chromatographed on silica gel

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

Procedure: A solution of ethyl 4-hydroxymandelate (19.6 g, 0.1 mol), 1,3-dibromopropane (60.75 g, 0.3 mol) and cesium carbonate (35.75 g, 0.11 mol) in dry DMF (200 mL) was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl. The organic layer was washed twice with water, once with brine and then dried over sodium sulfate. The organic layer was then filtered and the solvent remove in vacuo. The resulting oil was chromatographed on silica gel, using a gradient of 100% hexane to methylene chloride/hexane (2:1) to yield the titled compound. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl The organic layer was washed twice with water, once with brine dried over sodium sulfate The organic layer was then filtered the solvent remove in vacuo The resulting oil was chromatographed on silica gel

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

Procedure: 15.3 g of chromium trioxide is added dropwise to a solution of 15 g of ethyl 4-hydroxymandelate in 240 ml of acetic acid. The mixture is stirred at room temperature for 2 hours, poured into 1 l of ethyl acetate and extracted with saturated aqueous Na2CO3 solution. The aqueous phases are extracted with methylene chloride. The organic phases are washed with saturated aqueous Na2CO3 solution, followed by washing with water. The organic phases are dried over sodium sulfate. Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar)) give 4.04 g (27 wt %) ethyl 4-hydroxybenzoylformate as a yellow solid. extracted with saturated aqueous Na2CO3 solution The aqueous phases are extracted with methylene chloride The organic phases are washed with saturated aqueous Na2CO3 solution by washing with water The organic phases are dried over sodium sulfate Filtration, evaporation of the solvent and distillation (ball-tube still distillation, boiling point 205° C. (0.076 bar))

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5 g of 4-hydroxymandelic acid and 1.28 g of p-toluenesulfonic acid in 200 ml of ethanol is heated at 50° C. for 4 hours. The mixture is poured into saturated aqueous NaHCO3 solution, and a white precipitate is formed. The mixture is diluted with water until the precipitate disintegrates, and then is extracted with diethyl ether. The organic phases are dried over sodium sulfate. Filtration and evaporation of the solvent give ethyl 4-hydroxymandelate (4.2 g, 82%) as a pale yellowish solid. a white precipitate is formed is extracted with diethyl ether The organic phases are dried over sodium sulfate Filtration and evaporation of the solvent

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

Procedure: A solution of ethyl 4-hydroxymandelate (19.6 g, 0.1 mol), 1,3-dibromopropane (60.75 g, 0.3 mol) and cesium carbonate (35.75 g, 0.11 mol) in dry DMF (200 mL) was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl. The organic layer was washed twice with water, once with brine and then dried over sodium sulfate. The organic layer was then filtered and the solvent remove in vacuo. The resulting oil was chromatographed on silica gel, using a gradient of 100% hexane to methylene chloride/hexane (2:1) to yield the titled compound. The reaction mixture was partitioned between ethyl acetate and 1.0 N HCl The organic layer was washed twice with water, once with brine dried over sodium sulfate The organic layer was then filtered the solvent remove in vacuo The resulting oil was chromatographed on silica gel