Hydrochloric Acid → 2-Methanesulfonylbenzene-1-sulfonyl chloride

HRID 479081Notes

Reaction equation

HRID 479081 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]>[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

7

Reactant 4

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

Product 1

HCID 27351782-Methanesulfonylbenzene-1-sulfonyl chlorideYield 71%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

2-Methylsulfonylaniline (6.0 g; 0.035 mole) was added portionwise, with stirring, to a mixture of 30 mL of water and 30 mL of HCl. The mixture was cooled to 5° C. and sodium nitrite (2.7 g; 0.039 mole) dissolved in water (7 mL) was added dropwise maintaining the temperature between 0-5° C. After complete addition of sodium nitrite, the resulting solution was stirred at 0-5° C. for 30 minutes Sulfur dioxide was bubbled into 18 mL of HOAc for 14 min at room temperature. CuCl (0.8 g; 0.008 mole) was added and cooled to 10° C. Sulfur dioxide was bubbled through the suspension for an additional 15 min and the diazotized amine was added portionwise maintaining the temperature between 0-5° C. After the complete addition of 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 50 mL of water, filtered and washed three times with 10 mL of water to give, after drying in vacuum (30 in. Hg), 6.4 g (71% yield) of 2-methylsulfonylbenzenesulfonyl chloride which was characterized by its melting point and spectral data. 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 dropwise
  2. temperaturemaintaining the temperature between 0-5° C
  3. customwas bubbled into 18 mL of HOAc for 14 min at room temperature
  4. temperaturecooled to 10° C
  5. customSulfur dioxide was bubbled through the suspension for an additional 15 min
  6. additionthe diazotized amine was added portionwise
  7. temperaturemaintaining the temperature between 0-5° C
  8. additionAfter the complete addition of diazotized amine
  9. custombubbling of SO2
  10. additionAt the end of 3 hours, the suspension was diluted with 50 mL of water
  11. filtrationfiltered
  12. washwashed three times with 10 mL of water
  13. customto give

Sources & evidence

ORD record
ord-42a912a203d848ba934b05f22f2918de
Source dataset
uspto-grants-2003_11
Patent number
US06642416B2

Reaction notes

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