Hydrochloric Acid → 2-Methanesulfonylbenzene-1-sulfonyl chloride

HRID 479080Notes

Reaction equation

HRID 479080 reaction equation
[CH3:1][S:2]([C:5]1[CH:11]=[CH:10][CH:9]=[CH:8][C:6]=1N)(=[O:4])=[O:3].[ClH:12].N([O-])=O.[Na+].[S:17](=[O:19])=[O:18]>O.Cl[Cu].CC(O)=O>[CH3:1][S:2]([C:5]1[CH:11]=[CH:10][CH:9]=[CH:8][C:6]=1[S:17]([Cl:12])(=[O:19])=[O:18])(=[O:4])=[O:3]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 2446592-MethanesulfonylanilineHCID 23668193Sodium Nitrite2×

Product 1

HCID 27351782-Methanesulfonylbenzene-1-sulfonyl chlorideYield 61%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 176Acetic AcidSolvent3×HCID 962WaterSolvent2×

Conditions

Temperature
50 °C

Procedure

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%).

Workup

  1. additionwas added drop-wise
  2. temperaturemaintaining the temperature between 0-5° C
  3. stirringthe resulting solution was stirred for 30 minutes at 0-5° C
  4. temperaturecooled to 10° C
  5. customSulfur dioxide was bubbled through the suspension for an additional 15 minutes
  6. additionthe diazotized amine was added portionwise
  7. stirringwith stirring
  8. custombetween 0-5° C
  9. customSulfur dioxide was bubbled in continuously until the diazotized amine
  10. additionwas added completely
  11. additionAfter the complete addition of the diazotized amine
  12. custombubbling of SO2
  13. stirringthe green suspension was stirred at 0-5° C. for 3 hours
  14. additionAt the end of 3 hours, the suspension was diluted with water (300 mL)
  15. filtrationfiltered
  16. washthe solid washed three times with 50 mL of water
  17. customThe product was dried at room temperature in vacuum (30 in. Hg)

Sources & evidence

ORD record
ord-e5dfb8d0ea044e548501a9825f411bfd
Source dataset
uspto-grants-2003_11
Patent number
US06642416B2

Reaction notes

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