benzene-1,2-disulfonyl chloride

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 1,2-benzenedisulfonyl dichloride (72 mg, 0.26 mmol) and DCE (3 mL) at 40° C. was added a solution of tert-butyl (4-aminophenyl)(pyridin-2-ylmethyl)carbamate (78 mg, 0.26 mmol) and DBU (0.09 mL, 0.57 mmol) in dry DCE (2 mL). After 48 h, the heat was removed and the r×n was added to DCM:H2O (1:1, 5 mL) and the organic layer was separated. The aqueous layer was extracted with DCM (2×5 mL) and the collected organic layers were washed with Brine (5 mL), and dried over MgSO4. After filtration and concentration under reduced pressure, the residue was purified by preparative HPLC. The pure material was dissolved in DCM (1 mL) and 4M HCl in dioxane (0.5 mL) was added. After 3 h, the solvent was removed to provide 2-(4-((pyridin-2-ylmethyl)amino)phenyl)benzo[d][1,3,2]dithiazole 1,1,3,3-tetraoxide as an HCl Salt the heat was removed the r×n was added to DCM:H2O (1:1, 5 mL) the organic layer was separated The aqueous layer was extracted with DCM (2×5 mL) the collected organic layers were washed with Brine (5 mL) dried over MgSO4 After filtration and concentration under reduced pressure the residue was purified by preparative HPLC The pure material was dissolved in DCM (1 mL) 4M HCl in dioxane (0.5 mL) was added After 3 h the solvent was removed

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 1,2-benzenedisulfonyl dichloride (72 mg, 0.26 mmol) and DCE (3 mL) at 40° C. was added a solution of tert-butyl (4-aminophenyl)(pyridin-2-ylmethyl)carbamate (78 mg, 0.26 mmol) and DBU (0.09 mL, 0.57 mmol) in dry DCE (2 mL). After 48 h, the heat was removed and the r×n was added to DCM:H2O (1:1, 5 mL) and the organic layer was separated. The aqueous layer was extracted with DCM (2×5 mL) and the collected organic layers were washed with Brine (5 mL), and dried over MgSO4. After filtration and concentration under reduced pressure, the residue was purified by preparative HPLC. The pure material was dissolved in DCM (1 mL) and 4M HCl in dioxane (0.5 mL) was added. After 3 h, the solvent was removed to provide 2-(4-((pyridin-2-ylmethyl)amino)phenyl)benzo[d][1,3,2]dithiazole 1,1,3,3-tetraoxide as an HCl Salt the heat was removed the r×n was added to DCM:H2O (1:1, 5 mL) the organic layer was separated The aqueous layer was extracted with DCM (2×5 mL) the collected organic layers were washed with Brine (5 mL) dried over MgSO4 After filtration and concentration under reduced pressure the residue was purified by preparative HPLC The pure material was dissolved in DCM (1 mL) 4M HCl in dioxane (0.5 mL) was added After 3 h the solvent was removed

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Following the General Procedure (Scheme 1), tert-butyl 4-aminobenzoate, 1, (1.0 g, 5.17 mmol), triethylamine (1.8 mL, 12.9 mmol), dichloroethane (75 mL), benzene-1,2-disulfonyl dichloride (1.7 g, 2.88 mmol) and dichloroethane afforded tert-butyl-4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)benzoate, 5, (0.39 g, 38%).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Following the General Procedure (Scheme 1), tert-butyl 4-aminobenzoate, 1, (1.0 g, 5.17 mmol), triethylamine (1.8 mL, 12.9 mmol), dichloroethane (75 mL), benzene-1,2-disulfonyl dichloride (1.7 g, 2.88 mmol) and dichloroethane afforded tert-butyl-4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)benzoate, 5, (0.39 g, 38%).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of N-Boc-p-phenylenediamine (0.68 g, 3.26 mmol) and Et3N (0.51 mL, 7.19 mmol) in dry DCM (29 mL) was added to a refluxing solution of 1,2-benzenedisulfonyl dichloride (0.90 g, 3.27 mmol) in DCM (135 mL). After the addition was complete, the reaction solution was maintained at reflux for an additional 2 h. The heat was removed and after 16 h at rt, the solvent was removed under reduced pressure. The residue of the crude reaction mixture was dissolved in DCM and washed with saturated NaHCO3, brine, and dried. After filtration and concentration under reduced pressure yielding tert-butyl (4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)phenyl)carbamate, 1. After the addition the reaction solution was maintained at reflux for an additional 2 h The heat was removed and after 16 h at rt the solvent was removed under reduced pressure The residue of the crude reaction mixture washed with saturated NaHCO3, brine dried After filtration and concentration under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of N-Boc-p-phenylenediamine (0.68 g, 3.26 mmol) and Et3N (0.51 mL, 7.19 mmol) in dry DCM (29 mL) was added to a refluxing solution of 1,2-benzenedisulfonyl dichloride (0.90 g, 3.27 mmol) in DCM (135 mL). After the addition was complete, the reaction solution was maintained at reflux for an additional 2 h. The heat was removed and after 16 h at rt, the solvent was removed under reduced pressure. The residue of the crude reaction mixture was dissolved in DCM and washed with saturated NaHCO3, brine, and dried. After filtration and concentration under reduced pressure yielding tert-butyl (4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)phenyl)carbamate, 1. After the addition the reaction solution was maintained at reflux for an additional 2 h The heat was removed and after 16 h at rt the solvent was removed under reduced pressure The residue of the crude reaction mixture washed with saturated NaHCO3, brine dried After filtration and concentration under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 0.65 mol of ammonia in 1,050 ml of absolute ethanol is added dropwise, with stirring, to 0.13 mol of 1,2-benzenedisulphonyl chloride in 720 ml of absolute toluene at 25° C. The mixture is stirred a further hour, slight cloudiness is removed by filtration through a layer of kieselguhr, and the filtrate is evaporated to dryness. The ammonium salt of 1,3,2-benzodithiazole 1,1,3,3-tetroxide is obtained. slight cloudiness is removed by filtration through a layer of kieselguhr the filtrate is evaporated to dryness

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 0.65 mol of ammonia in 1,050 ml of absolute ethanol is added dropwise, with stirring, to 0.13 mol of 1,2-benzenedisulphonyl chloride in 720 ml of absolute toluene at 25° C. The mixture is stirred a further hour, slight cloudiness is removed by filtration through a layer of kieselguhr, and the filtrate is evaporated to dryness. The ammonium salt of 1,3,2-benzodithiazole 1,1,3,3-tetroxide is obtained. slight cloudiness is removed by filtration through a layer of kieselguhr the filtrate is evaporated to dryness

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 1,2-benzenedisulfonyl dichloride (72 mg, 0.26 mmol) and DCE (3 mL) at 40° C. was added a solution of tert-butyl (4-aminophenyl)(pyridin-2-ylmethyl)carbamate (78 mg, 0.26 mmol) and DBU (0.09 mL, 0.57 mmol) in dry DCE (2 mL). After 48 h, the heat was removed and the r×n was added to DCM:H2O (1:1, 5 mL) and the organic layer was separated. The aqueous layer was extracted with DCM (2×5 mL) and the collected organic layers were washed with Brine (5 mL), and dried over MgSO4. After filtration and concentration under reduced pressure, the residue was purified by preparative HPLC. The pure material was dissolved in DCM (1 mL) and 4M HCl in dioxane (0.5 mL) was added. After 3 h, the solvent was removed to provide 2-(4-((pyridin-2-ylmethyl)amino)phenyl)benzo[d][1,3,2]dithiazole 1,1,3,3-tetraoxide as an HCl Salt the heat was removed the r×n was added to DCM:H2O (1:1, 5 mL) the organic layer was separated The aqueous layer was extracted with DCM (2×5 mL) the collected organic layers were washed with Brine (5 mL) dried over MgSO4 After filtration and concentration under reduced pressure the residue was purified by preparative HPLC The pure material was dissolved in DCM (1 mL) 4M HCl in dioxane (0.5 mL) was added After 3 h the solvent was removed

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Following the General Procedure (Scheme 1), tert-butyl 4-aminobenzoate, 1, (1.0 g, 5.17 mmol), triethylamine (1.8 mL, 12.9 mmol), dichloroethane (75 mL), benzene-1,2-disulfonyl dichloride (1.7 g, 2.88 mmol) and dichloroethane afforded tert-butyl-4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)benzoate, 5, (0.39 g, 38%).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of N-Boc-p-phenylenediamine (0.68 g, 3.26 mmol) and Et3N (0.51 mL, 7.19 mmol) in dry DCM (29 mL) was added to a refluxing solution of 1,2-benzenedisulfonyl dichloride (0.90 g, 3.27 mmol) in DCM (135 mL). After the addition was complete, the reaction solution was maintained at reflux for an additional 2 h. The heat was removed and after 16 h at rt, the solvent was removed under reduced pressure. The residue of the crude reaction mixture was dissolved in DCM and washed with saturated NaHCO3, brine, and dried. After filtration and concentration under reduced pressure yielding tert-butyl (4-(1,1,3,3-tetraoxidobenzo[d][1,3,2]dithiazol-2-yl)phenyl)carbamate, 1. After the addition the reaction solution was maintained at reflux for an additional 2 h The heat was removed and after 16 h at rt the solvent was removed under reduced pressure The residue of the crude reaction mixture washed with saturated NaHCO3, brine dried After filtration and concentration under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In 5 mL of dichloromethane, 117 mg (0.30 mmol) of 6β-amino-17-cyclopropylmethyl-4,5α-epoxy-3-methoxymethoxy-morphinan-14-ol was dissolved, and 0.04 mL (0.29 mmol) of triethylamine and 79 mg (0.31 mmol) of benzene-1,2-disulfonyl dichloride were added, followed by heating the mixture to reflux for 1 hour. After allowing the reaction solution to cool to room temperature, aqueous saturated sodium hydrogen carbonate solution was added to the reaction mixture, and the resulting mixture was extracted with chloroform. Organic layers were combined, washed with saturated saline, dried over anhydrous magnesium sulfate and concentrated to obtain 192 mg of 2-(17-cyclopropylmethyl-4,5α-epoxy-14-hydroxy-3-methoxymethoxy-morphinan-6β-yl)-benzo[1,3,2]dithiazol-1,1,3,3-tetroxide as a crude product. by heating the mixture to reflux for 1 hour the resulting mixture was extracted with chloroform washed with saturated saline dried over anhydrous magnesium sulfate concentrated