4-Aminophenol → HCID 21951489, compound

HRID 1760348Notes

Reaction equation

HRID 1760348 reaction equation
F[C:2]1[CH:7]=[C:6](F)[CH:5]=[CH:4][C:3]=1[P:9](=[O:22])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[NH2:23][C:24]1[CH:29]=[CH:28][C:27]([OH:30])=[CH:26][CH:25]=1.C(=O)([O-])[O-].[K+].[K+].C[N:38]1[C:42](=[O:43])[CH2:41][CH2:40][CH2:39]1.[C:44]1(C)C=CC=C[CH:45]=1>>[NH2:23][C:24]1[CH:29]=[CH:28][C:27]([O:30][C:2]2[CH:7]=[C:6]([O:43][C:42]3[CH:45]=[CH:44][C:39]([NH2:38])=[CH:40][CH:41]=3)[CH:5]=[CH:4][C:3]=2[P:9](=[O:22])([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:26][CH:25]=1

Participants

6

Reactant 5

HCID 4034-AminophenolHCID 1140TolueneHCID 11430Potassium CarbonateHCID 13387N-methyl-2-pyrrolidoneHCID 21951492(2,4-Difluorophenyl)(oxo)diphenyl-lambda~5~-phosphane

Product 1

HCID 21951489HCID 21951489, compound

Conditions

Temperature
135 °C

Procedure

Into a 500 mL three neck round bottom flask equipped with a mechanical stirrer, thermometer and a Dean-Stark trap equipped with a drying tube was placed 2,4-difluorophenyldiphenylphosphine oxide (12.00 g, 0.0382 mole), 4-aminophenol (8.6673 g, 0.0794 mol), potassium carbonate (13.1682 g, 0.0953 mol), NMP (85 mL) and toluene (25 mL). The mixture was heated to 135° C. while removing water via azeotropic distillation. After 16 hours, the toluene was removed from the reaction and the resulting solution was heated at 165° C. for 4 hours. The reaction mixture was cooled to room temperature and then poured into 1 L of 5% acetic acid (aq) with vigorous stirring. A tan solid formed after stirring for 45 minutes. The crude tan solid was collected via filtration, washed with excess water, and dried in an oven at 110° C. to give 16.76 g (89% crude yield). The solid was recrystallized from a dimethylacetamide/water solution (3:1) and light tan needles were obtained. The solid exhibited a melting point of 271.5-274.7° C. as determined by DSC at a heating rate of 10° C./min. Mass spectroscopic analysis: M+492 [C30H25N2O3P+]

Workup

  1. customthermometer and a Dean-Stark trap equipped with a drying tube
  2. customwhile removing water
  3. distillationvia azeotropic distillation
  4. customthe toluene was removed from the reaction
  5. temperaturethe resulting solution was heated at 165° C. for 4 hours
  6. temperatureThe reaction mixture was cooled to room temperature
  7. additionpoured into 1 L of 5% acetic acid (aq) with vigorous stirring
  8. customA tan solid formed
  9. filtrationThe crude tan solid was collected via filtration
  10. washwashed with excess water
  11. customdried in an oven at 110° C.
  12. customto give 16.76 g (89% crude yield)
  13. customThe solid was recrystallized from a dimethylacetamide/water solution (3:1)
  14. customlight tan needles were obtained

Sources & evidence

ORD record
ord-ff4d96764ab8451ab2bd3df2cdc2187a
Source dataset
uspto-grants-2005_01
Patent number
US06841652B2

Reaction notes

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