2-bromobenzene-1,3-diol

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: To a solution of 2-bromo-1,3-benzenediol (3.028 g, 16.02 mmol) in dichloromethane (70 ml), TEA (3.35 ml, 24.03 mmol) and acetic anhydride (1.512 ml, 16.02 mmol) were added under stirring. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with a saturated solution of ammonium chloride (100 ml), and extracted with ethyl acetate (3 times 70 ml). The combined organic layers were dried over sodium sulphate, filtered and evaporated to afford the title compound as a black oil which was used directly used in the next step. (3.028 g) The reaction mixture was stirred at room temperature overnight The reaction was quenched with a saturated solution of ammonium chloride (100 ml) extracted with ethyl acetate (3 times 70 ml) The combined organic layers were dried over sodium sulphate filtered evaporated

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

Procedure: To a solution of 2-bromo-1,3-benzenediol (3.028 g, 16.02 mmol) in dichloromethane (70 ml), TEA (3.35 ml, 24.03 mmol) and acetic anhydride (1.512 ml, 16.02 mmol) were added under stirring. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with a saturated solution of ammonium chloride (100 ml), and extracted with ethyl acetate (3 times 70 ml). The combined organic layers were dried over sodium sulphate, filtered and evaporated to afford the title compound as a black oil which was used directly used in the next step. (3.028 g) The reaction mixture was stirred at room temperature overnight The reaction was quenched with a saturated solution of ammonium chloride (100 ml) extracted with ethyl acetate (3 times 70 ml) The combined organic layers were dried over sodium sulphate filtered evaporated

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes

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

Procedure: To a solution of 2-bromo-1,3-benzenediol (3.028 g, 16.02 mmol) in dichloromethane (70 ml), TEA (3.35 ml, 24.03 mmol) and acetic anhydride (1.512 ml, 16.02 mmol) were added under stirring. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with a saturated solution of ammonium chloride (100 ml), and extracted with ethyl acetate (3 times 70 ml). The combined organic layers were dried over sodium sulphate, filtered and evaporated to afford the title compound as a black oil which was used directly used in the next step. (3.028 g) The reaction mixture was stirred at room temperature overnight The reaction was quenched with a saturated solution of ammonium chloride (100 ml) extracted with ethyl acetate (3 times 70 ml) The combined organic layers were dried over sodium sulphate filtered evaporated

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

Procedure: To a solution of 2-bromo-1,3-benzenediol (3.028 g, 16.02 mmol) in dichloromethane (70 ml), TEA (3.35 ml, 24.03 mmol) and acetic anhydride (1.512 ml, 16.02 mmol) were added under stirring. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with a saturated solution of ammonium chloride (100 ml), and extracted with ethyl acetate (3 times 70 ml). The combined organic layers were dried over sodium sulphate, filtered and evaporated to afford the title compound as a black oil which was used directly used in the next step. (3.028 g) The reaction mixture was stirred at room temperature overnight The reaction was quenched with a saturated solution of ammonium chloride (100 ml) extracted with ethyl acetate (3 times 70 ml) The combined organic layers were dried over sodium sulphate filtered evaporated

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

Procedure: To a solution of 2-bromo-1,3-benzenediol (3.028 g, 16.02 mmol) in dichloromethane (70 ml), TEA (3.35 ml, 24.03 mmol) and acetic anhydride (1.512 ml, 16.02 mmol) were added under stirring. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with a saturated solution of ammonium chloride (100 ml), and extracted with ethyl acetate (3 times 70 ml). The combined organic layers were dried over sodium sulphate, filtered and evaporated to afford the title compound as a black oil which was used directly used in the next step. (3.028 g) The reaction mixture was stirred at room temperature overnight The reaction was quenched with a saturated solution of ammonium chloride (100 ml) extracted with ethyl acetate (3 times 70 ml) The combined organic layers were dried over sodium sulphate filtered evaporated

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

Procedure: Bromine (0.363 L) was added dropwise over 2 hours to a solution of resorcinol (250 g) in dichloromethane (3.5 L). The solution was stirred at room temperature for 18 hours at which time approximately 1 L of the dichloromethane was removed by distillation. MeOH was added and the distillation continued in this manner until all of the dichloromethane was removed and the solution contained approximately 1.5 L of MeOH. To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L). The resulting mixture was stirred at ambient temperature for 1 hour. The solution was then acidified to pH=2 with concentrated HCl (75 mL) and extracted with tert-butyl methyl ether (TBME) (2×1 L). The combined organic layers were treated with activated charcoal (20 g) and filtered through Celite; the Celite was washed with an additional 500 mL of TBME. The solvent was then removed in vacuo. The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate and filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes yielding 2-bromoresorcinol (122 g). m.p. 86-88°. was removed by distillation MeOH was added the distillation was removed To this was added a solution of NaOH (181.5 g) and Na2SO3 (573 g) in H2O (7.5 L) extracted with tert-butyl methyl ether (TBME) (2×1 L) The combined organic layers were treated with activated charcoal (20 g) filtered through Celite the Celite was washed with an additional 500 mL of TBME The solvent was then removed in vacuo The resulting crude 2-bromoresorcinol was dissolved in a minimum amount of ethyl acetate filtered through silica gel eluting with a gradient from 20% to 40% ethyl acetate in hexanes