1-(5-chloro-2,4-dihydroxyphenyl)ethanone

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

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

Procedure: Benzyl bromide (17.5 ml, 0.147 mol) was added to a mixture of 1-(5-chloro-2,4-dihydroxyphenyl)ethanone (11 g, 0.059 mol) and potassium carbonate (20.34 g, 0.147 mol) in acetonitrile (180 ml). The mixture was stirred at reflux for 6 h and then allowed to cool to RT and stirred overnight. The mixture was filtered, and the solid residue was rinsed with DCM (3×50 ml). The combined organic filtrates were evaporated under vacuo to give a pale yellow solid. The latter was triturated with a mixture of hexane/EtOAc (175/7.5) and filtered to afford the title compound 1-[2,4-bis(benzyloxy)-5-chlorophenyl]ethanone (20.4 g, 93% yield) as an off-white solid. at reflux for 6 h stirred overnight The mixture was filtered the solid residue was rinsed with DCM (3×50 ml) The combined organic filtrates were evaporated under vacuo to give a pale yellow solid The latter was triturated with a mixture of hexane/EtOAc (175/7.5) filtered

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Acetic acid (17.5 ml) was added dropwise to a suspension of 4-chlorobenzene-1,3-diol (20 g, 0.138 mol) in BF3.OEt2 (100 ml) under a nitrogen atmosphere. The reaction mixture was stirred at 90° C. for 3.5 h and then allowed to cool to RT, causing a solid to precipitate. The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml). This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered, washed with water, and air-dried overnight to afford the title compound 1-(5-chloro-2,4-dihydroxyphenyl)-ethanone (11.3 g, 44%). to cool to RT to precipitate The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml) This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered washed with water air-dried overnight

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

Procedure: Benzyl bromide (30 mL) was added to a mixture of 1-(5-chloro-2,4-dihydroxy-phenyl)-ethanone (20 g, 0.107 moles) and potassium carbonate (37 g, 2.5 equiv) in acetonitrile (350 mL). The mixture was heated at reflux for 6 hours then allowed to cool and stirred overnight. The mixture was filtered and the solids were washed with dichloromethane (3×100 mL). The combined organic extracts were evaporated in vacuo to leave a pale yellow solid which was triturated with a mixture of hexane (350 mL)/ethyl acetate (15 mL) and filtered to give an off-white solid, 1-(2,4-bis-benzyloxy-5-chloro-phenyl)-ethanone (35.4 g, 90%). 1H NMR (400 MHz) consistent with structure. The mixture was heated at reflux for 6 hours to cool The mixture was filtered the solids were washed with dichloromethane (3×100 mL) The combined organic extracts were evaporated in vacuo to leave a pale yellow solid which was triturated with a mixture of hexane (350 mL)/ethyl acetate (15 mL) filtered

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Acetic acid (17.5 mL) was added dropwise to a suspension of 4-chlororesorcinol (42.5 g, 0.293 mmol) in boron trifluoride etherate (200 mL) under a nitrogen atmosphere. The reaction mixture was heated at 90° C. for 3.5 hours and then allowed to cool to room temperature. A solid had formed after around 1 hour of cooling. The mixture was poured into 700 mL of a 10% w/v aqueous sodium acetate solution. This mixture was stirred vigorously for 2.5 hours. A light brown solid had formed which was filtered, washed with water and air-dried overnight to afford 1-(5-chloro-2,4-dihydroxy-phenyl)-ethanone (31.6 g, 58%). LCMS: [M−H]+ 185. to cool to room temperature A solid had formed after around 1 hour of cooling A light brown solid had formed which was filtered washed with water air-dried overnight

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

Procedure: Benzyl bromide (17.5 ml, 0.147 mol) was added to a mixture of 1-(5-chloro-2,4-dihydroxyphenyl)ethanone (11 g, 0.059 mol) and potassium carbonate (20.34 g, 0.147 mol) in acetonitrile (180 ml). The mixture was stirred at reflux for 6 h and then allowed to cool to RT and stirred overnight. The mixture was filtered, and the solid residue was rinsed with DCM (3×50 ml). The combined organic filtrates were evaporated under vacuo to give a pale yellow solid. The latter was triturated with a mixture of hexane/EtOAc (175/7.5) and filtered to afford the title compound 1-[2,4-bis(benzyloxy)-5-chlorophenyl]ethanone (20.4 g, 93% yield) as an off-white solid. at reflux for 6 h stirred overnight The mixture was filtered the solid residue was rinsed with DCM (3×50 ml) The combined organic filtrates were evaporated under vacuo to give a pale yellow solid The latter was triturated with a mixture of hexane/EtOAc (175/7.5) filtered

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

Procedure: Benzyl bromide (17.5 ml, 0.147 mol) was added to a mixture of 1-(5-chloro-2,4-dihydroxyphenyl)ethanone (11 g, 0.059 mol) and potassium carbonate (20.34 g, 0.147 mol) in acetonitrile (180 ml). The mixture was stirred at reflux for 6 h and then allowed to cool to RT and stirred overnight. The mixture was filtered, and the solid residue was rinsed with DCM (3×50 ml). The combined organic filtrates were evaporated under vacuo to give a pale yellow solid. The latter was triturated with a mixture of hexane/EtOAc (175/7.5) and filtered to afford the title compound 1-[2,4-bis(benzyloxy)-5-chlorophenyl]ethanone (20.4 g, 93% yield) as an off-white solid. at reflux for 6 h stirred overnight The mixture was filtered the solid residue was rinsed with DCM (3×50 ml) The combined organic filtrates were evaporated under vacuo to give a pale yellow solid The latter was triturated with a mixture of hexane/EtOAc (175/7.5) filtered

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Acetic acid (17.5 ml) was added dropwise to a suspension of 4-chlorobenzene-1,3-diol (20 g, 0.138 mol) in BF3.OEt2 (100 ml) under a nitrogen atmosphere. The reaction mixture was stirred at 90° C. for 3.5 h and then allowed to cool to RT, causing a solid to precipitate. The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml). This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered, washed with water, and air-dried overnight to afford the title compound 1-(5-chloro-2,4-dihydroxyphenyl)-ethanone (11.3 g, 44%). to cool to RT to precipitate The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml) This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered washed with water air-dried overnight

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Acetic acid (17.5 ml) was added dropwise to a suspension of 4-chlorobenzene-1,3-diol (20 g, 0.138 mol) in BF3.OEt2 (100 ml) under a nitrogen atmosphere. The reaction mixture was stirred at 90° C. for 3.5 h and then allowed to cool to RT, causing a solid to precipitate. The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml). This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered, washed with water, and air-dried overnight to afford the title compound 1-(5-chloro-2,4-dihydroxyphenyl)-ethanone (11.3 g, 44%). to cool to RT to precipitate The mixture was poured into a 10% w/v aqueous sodium acetate solution (350 ml) This mixture was then stirred vigorously for 2.5 h to afford a light brown solid, which was filtered washed with water air-dried overnight

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

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

Procedure: Benzyl bromide (30 mL) was added to a mixture of 1-(5-chloro-2,4-dihydroxy-phenyl)-ethanone (20 g, 0.107 moles) and potassium carbonate (37 g, 2.5 equiv) in acetonitrile (350 mL). The mixture was heated at reflux for 6 hours then allowed to cool and stirred overnight. The mixture was filtered and the solids were washed with dichloromethane (3×100 mL). The combined organic extracts were evaporated in vacuo to leave a pale yellow solid which was triturated with a mixture of hexane (350 mL)/ethyl acetate (15 mL) and filtered to give an off-white solid, 1-(2,4-bis-benzyloxy-5-chloro-phenyl)-ethanone (35.4 g, 90%). 1H NMR (400 MHz) consistent with structure. The mixture was heated at reflux for 6 hours to cool The mixture was filtered the solids were washed with dichloromethane (3×100 mL) The combined organic extracts were evaporated in vacuo to leave a pale yellow solid which was triturated with a mixture of hexane (350 mL)/ethyl acetate (15 mL) filtered

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Acetic acid (17.5 mL) was added dropwise to a suspension of 4-chlororesorcinol (42.5 g, 0.293 mmol) in boron trifluoride etherate (200 mL) under a nitrogen atmosphere. The reaction mixture was heated at 90° C. for 3.5 hours and then allowed to cool to room temperature. A solid had formed after around 1 hour of cooling. The mixture was poured into 700 mL of a 10% w/v aqueous sodium acetate solution. This mixture was stirred vigorously for 2.5 hours. A light brown solid had formed which was filtered, washed with water and air-dried overnight to afford 1-(5-chloro-2,4-dihydroxy-phenyl)-ethanone (31.6 g, 58%). LCMS: [M−H]+ 185. to cool to room temperature A solid had formed after around 1 hour of cooling A light brown solid had formed which was filtered washed with water air-dried overnight