Hydrochloric Acid → 2-Methanesulfonylbenzene-1-sulfonyl chloride

Participants

Reaction Conditions

Reaction Steps

2-Methylsulfonylaniline (48 g, 0.28 mole), was added portion-wise with stirring to 365 mL of water, 250 mL of conc. HCl and 60 mL of HOAc. The mixture was cooled to 50° C. and sodium nitrite (22.3 g; 0.32 mole) dissolved in 250 mL water, was added drop-wise with stirring maintaining the temperature between 0-5° C. After complete addition of sodium nitrite, the resulting solution was stirred for 30 minutes at 0-5° C. Sulfur dioxide was bubbled into 200 mL of glacial acetic acid at room temperature for 10 minutes CuCl2·2H2O (11 g; 0.06 mole) and CuCl (3.7 g; 0.037 mole) were added to the HOAc and cooled to 10° C. Sulfur dioxide was bubbled through the suspension for an additional 15 minutes and the diazotized amine was added portionwise with stirring keeping the temperature between 0-5° C. Sulfur dioxide was bubbled in continuously until the diazotized amine was added completely. After the complete addition of the diazotized amine, bubbling of SO2 was stopped and the green suspension was stirred at 0-5° C. for 3 hours. At the end of 3 hours, the suspension was diluted with water (300 mL), filtered and the solid washed three times with 50 mL of water. The product was dried at room temperature in vacuum (30 in. Hg) to give 46 g of 2-methylsulfonylbenzenesulfonyl chloride (61% yield) as a white solid. mp 135-137° C. (lit. 133-135° C.). 1H NMR (CDCl3) δ 8.3-8.6 (m, 2H), 7.87-8.02 (m, 2H), 3.41 (s, 3H). 13C NMR (CDCl3) δ 142.94, 139.24, 136.61, 135.22, 133.58, 132.13, 45.49. CIMS (m/e) 255 (M+H+, 100%).

Provenance & Evidence