2,5-dibromobenzenesulfonyl chloride

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

Procedure: Inside a glove box, a 100 mL round-bottom flask equipped with a reflux condenser, stirring bar, and septum was charged with 2,5-dibromo-benzene-sulfonyl chloride (16.35 g, 50 mmoles), trifluoromethanesulfonamide (7.27 g, 50 mmoles), and acetonitrile (50 mL). Triethylamine (14 mL, 100 mmoles) was added slowly by syringe. The solution was heated to a reflux overnight. The solution was cooled to room temperature and poured into an aqueous solution of sodium hydroxide (4.0 g, 100 mmoles) in 100 mL water. The solvents were evaporated on a rotary evaporator and the solids were dried under vacuum. The solids were recrystallized by dissolving in dioxane at a reflux, treating with decolorizing carbon, filtering the solution, and concentrating the solution at a reflux to 130 mL to induce crystallization. The white crystals were collected by vacuum filtration, washed with dioxane, and dried under vacuum. The recrystallization was repeated to give 19.45 g (83% yield) of N-trifluoromethanesulfonyl-2,5-dibromo-benzene-sulfonamide, sodium salt. The salt was dried overnight in a vacuum oven at 150° C. under a nitrogen purge. Inside a glove box, a 100 mL round-bottom flask equipped with a reflux condenser The solution was heated to a reflux overnight The solvents were evaporated on a rotary evaporator the solids were dried under vacuum The solids were recrystallized by dissolving in dioxane at a reflux treating with decolorizing carbon filtering the solution concentrating the solution at a reflux to 130 mL crystallization The white crystals were collected by vacuum filtration washed with dioxane dried under vacuum The recrystallization

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

Procedure: Inside a glove box, a 200 mL round-bottom flask equipped with a reflux condenser, stirring bar, and septum was charged with 2,5-dibromo-benzene-sulfonyl chloride (16.72 g, 50 mmoles), trifluoromethanesulfonamide (7.45 g, 50 mmoles), and acetonitrile (50 mL). Triethylamine (14 mL, 100 mmoles) was added slowly by syringe. The solution was heated to a reflux overnight. The solution was cooled to room temperature and poured into an aqueous solution of sodium hydroxide (4.0 g, 100 mmoles) in 100 mL water. The solvents were evaporated on a rotary evaporator and the solids were dried under vacuum. The solids were dissolved in n-propanol at reflux, treated with decolorizing carbon, filtered to remove the carbon and residual salts, evaporated on a rotary evaporator, and dried under vacuum to give 23.54 g (100%). The solids were recrystallized from dioxane to give 12.77 g (54% yield) of N-trifluoromethanesulfonyl-2,5-dibromo-benzene-sulfonamide, sodium salt. The salt was dried overnight in a vacuum oven at 150° C. under a nitrogen purge. 1H NMR (DMSO-d6): 7.62 (dd, J=8 and 2 Hz, 1H), 7.69 (d, J=8 Hz, 1H), 8.05 (d, J=2 Hz, 1H). Inside a glove box, a 200 mL round-bottom flask equipped with a reflux condenser The solution was heated to a reflux overnight The solvents were evaporated on a rotary evaporator the solids were dried under vacuum The solids were dissolved in n-propanol at reflux treated with decolorizing carbon filtered to remove the carbon and residual salts evaporated on a rotary evaporator dried under vacuum to give 23.54 g (100%) The solids were recrystallized from dioxane

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

Procedure: A modification of the published procedures of Moroni et al. in Macromolecules 1994, 27, 562 was used. A 300 mL round-bottom flask equipped with a reflux condenser, stirring bar, and gas inlet was charged with 1,4-dibromobenzene (50 g, 0.21 moles) and chlorosulfonic acid (100 mL). The mixture was heated to 90° C. for 2 hours under nitrogen to give a clear solution. The solution was cooled to room temperature and carefully poured onto ice (1 kg) to give a precipitate. The solids were collected by vacuum filtration, washed well with water, and air dried on the filter then dried under vacuum at 50° C. to give 68.36 g. The product was recrystallized from cyclohexane after treating with decolorizing carbon, collected by vacuum filtration, and dried at 50° C. under vacuum to give 55.37 g (79% yield) of 2,5-dibromobenzenesulfonyl chloride. 1H NMR (CDCl3): 7.66 (dd, 8.4, 2.3 Hz, 1H), 7.72 (d, 8.4 Hz, 1H), 8.30 (d, 2.3 Hz, 1H). A 300 mL round-bottom flask equipped with a reflux condenser to give a clear solution The solution was cooled to room temperature carefully poured onto ice (1 kg) to give a precipitate The solids were collected by vacuum filtration washed well with water, and air dried on the filter then dried under vacuum at 50° C. to give 68.36 g The product was recrystallized from cyclohexane after treating with decolorizing carbon collected by vacuum filtration dried at 50° C. under vacuum

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

Procedure: Inside a glove box, a 100 mL round-bottom flask equipped with a reflux condenser, stirring bar, and septum was charged with 2,5-dibromo-benzene-sulfonyl chloride (16.35 g, 50 mmoles), trifluoromethanesulfonamide (7.27 g, 50 mmoles), and acetonitrile (50 mL). Triethylamine (14 mL, 100 mmoles) was added slowly by syringe. The solution was heated to a reflux overnight. The solution was cooled to room temperature and poured into an aqueous solution of sodium hydroxide (4.0 g, 100 mmoles) in 100 mL water. The solvents were evaporated on a rotary evaporator and the solids were dried under vacuum. The solids were recrystallized by dissolving in dioxane at a reflux, treating with decolorizing carbon, filtering the solution, and concentrating the solution at a reflux to 130 mL to induce crystallization. The white crystals were collected by vacuum filtration, washed with dioxane, and dried under vacuum. The recrystallization was repeated to give 19.45 g (83% yield) of N-trifluoromethanesulfonyl-2,5-dibromo-benzene-sulfonamide, sodium salt. The salt was dried overnight in a vacuum oven at 150° C. under a nitrogen purge. Inside a glove box, a 100 mL round-bottom flask equipped with a reflux condenser The solution was heated to a reflux overnight The solvents were evaporated on a rotary evaporator the solids were dried under vacuum The solids were recrystallized by dissolving in dioxane at a reflux treating with decolorizing carbon filtering the solution concentrating the solution at a reflux to 130 mL crystallization The white crystals were collected by vacuum filtration washed with dioxane dried under vacuum The recrystallization

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

Procedure: Inside a glove box, a 200 mL round-bottom flask equipped with a reflux condenser, stirring bar, and septum was charged with 2,5-dibromo-benzene-sulfonyl chloride (16.72 g, 50 mmoles), trifluoromethanesulfonamide (7.45 g, 50 mmoles), and acetonitrile (50 mL). Triethylamine (14 mL, 100 mmoles) was added slowly by syringe. The solution was heated to a reflux overnight. The solution was cooled to room temperature and poured into an aqueous solution of sodium hydroxide (4.0 g, 100 mmoles) in 100 mL water. The solvents were evaporated on a rotary evaporator and the solids were dried under vacuum. The solids were dissolved in n-propanol at reflux, treated with decolorizing carbon, filtered to remove the carbon and residual salts, evaporated on a rotary evaporator, and dried under vacuum to give 23.54 g (100%). The solids were recrystallized from dioxane to give 12.77 g (54% yield) of N-trifluoromethanesulfonyl-2,5-dibromo-benzene-sulfonamide, sodium salt. The salt was dried overnight in a vacuum oven at 150° C. under a nitrogen purge. 1H NMR (DMSO-d6): 7.62 (dd, J=8 and 2 Hz, 1H), 7.69 (d, J=8 Hz, 1H), 8.05 (d, J=2 Hz, 1H). Inside a glove box, a 200 mL round-bottom flask equipped with a reflux condenser The solution was heated to a reflux overnight The solvents were evaporated on a rotary evaporator the solids were dried under vacuum The solids were dissolved in n-propanol at reflux treated with decolorizing carbon filtered to remove the carbon and residual salts evaporated on a rotary evaporator dried under vacuum to give 23.54 g (100%) The solids were recrystallized from dioxane