Phenol → Phenylsulfamate

HRID 1893616Notes

Reaction equation

HRID 1893616 reaction equation
Cl[S:2]([N:5]=C=O)(=[O:4])=[O:3].S(Cl)(=O)(=O)N.[C:13]1([OH:19])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[Na+].[Cl-]>CN1C(=O)CCC1.C(O)=O>[C:13]1([O:19][S:2](=[O:3])(=[O:4])[NH2:5])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 996PhenolHCID 5234Sodium ChlorideHCID 24499Chlorosulfamic acidHCID 70918Chlorosulfonyl isocyanate

Product 1

HCID 11030308PhenylsulfamateYield 81%

Reagents, catalysts & solvents 2

HCID 284Formic AcidSolvent2×HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
0 °C

Procedure

A three necked round bottom equipped with a reflux condensor was charged with chlorosulfonyl isocyanate (5.25 ml, 0.06 mol) and cooled to 0° C. Formic acid (2.25 mL, 0.06 mol) was added dropwise with rapid stirring with rapid gas evolution observed. Upon complete addition of formic acid, the reaction was let warm to room temperature. After 2 h, the resultant reaction vessel containing the solid sulfamoyl chloride was cooled to 0° C. and phenol (1.88 g, 0.02 mol) dissolved in NMP (25 mL) was added dropwise via an addition funnel. The reaction was let warm to room temperature. After 3 h stirring, the reaction mixture was poured into cold saturated aqueous NaCl (120 mL) and extracted with EtOAc. After removal of the separated organic solvent, the crude product was purified by column chromatography on silica (35% EtOAc/hexane) to provide sulfamic acid phenyl ester (2.8 g, 81%): LCMS found 173.9 [M+H]+.

Workup

  1. customA three necked round bottom equipped with a reflux condensor
  2. temperaturethe reaction was let warm to room temperature
  3. customthe resultant reaction vessel
  4. temperaturewas cooled to 0° C.
  5. additionwas added dropwise via an addition funnel
  6. temperatureThe reaction was let warm to room temperature
  7. stirringAfter 3 h stirring
  8. extractionextracted with EtOAc
  9. customAfter removal of the separated organic solvent
  10. customthe crude product was purified by column chromatography on silica (35% EtOAc/hexane)

Sources & evidence

ORD record
ord-5de93f67d665429eb9ed8b6a3d094774
Source dataset
uspto-grants-2013_08
Patent number
US08513186B2

Reaction notes

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