Urea → 3-hydroxy-N-methylbenzenesulfonamide

HRID 902719Notes

Reaction equation

HRID 902719 reaction equation
[CH3:1][NH:2][S:3]([C:6]1[CH:11]=[CH:10][CH:9]=[C:8](N)[CH:7]=1)(=[O:5])=[O:4].N([O-])=[O:14].[Na+].NC(N)=O>O.OS(O)(=O)=O>[CH3:1][NH:2][S:3]([C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([OH:14])[CH:7]=1)(=[O:5])=[O:4]

Participants

6

Reactant 3

HCID 1176UreaHCID 72048903-amino-N-methylbenzenesulfonamideHCID 23668193Sodium Nitrite

Product 1

HCID 206215543-hydroxy-N-methylbenzenesulfonamide

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 1118Sulfuric AcidSolvent

Procedure

N-Methyl-3-aminobenzene sulfonamide (488 mg, 2.62 mmole) was dissolved in a mixture of 10 mL of H2O and 2 mL of conc. H2SO4, and was cooled to −5°. A solution of NaNO2 (207 mg, 3 mmole) in 2 mL of H2O was added dropwise at such a rate that the temperature doesn't exceed 0°. The reaction was stirred for 10 minutes, urea (100 mg) was added, and the reaction was stirred an additional 10 minutes. The cold solution of diazo compound was slowly added with stirring to a 0° solution of Cu(NO3)2 dihydrate (10.3 g, 43 mmole) and Cu2O (363 mg) in 100 mL of H2O. Stirring was continued for 30 minutes as the temperature was allowed to warm to 23°. The heterogeneous reaction was extracted with Et2O, and the extracts were extracted with 0.2N NaOH. The basic extracts were washed with Et2O, acidified, and extracted with CH2Cl2. The extracts were dried, and the solvent removed. The residue was chromatographed on a silica gel column, and elution with 50% EtOAc in hexane gave the titled product, 175 mg (36%). MS (ESI) 188 (MH+).

Workup

  1. temperaturewas cooled to −5°
  2. stirringthe reaction was stirred an additional 10 minutes
  3. stirringStirring
  4. waitwas continued for 30 minutes as the temperature
  5. temperatureto warm to 23°
  6. customThe heterogeneous reaction
  7. extractionwas extracted with Et2O
  8. extractionthe extracts were extracted with 0.2N NaOH
  9. washThe basic extracts were washed with Et2O
  10. extractionextracted with CH2Cl2
  11. customThe extracts were dried
  12. customthe solvent removed
  13. customThe residue was chromatographed on a silica gel column, and elution with 50% EtOAc in hexane

Sources & evidence

ORD record
ord-a6222294c91b49d8b0753cff27280aaa
Source dataset
uspto-grants-2008_04
Patent number
US07365085B2

Reaction notes

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