Phenol → BPA phosphate

HRID 51172

Reaction equation

HRID 51172 reaction equation
[CH3:1][C:2]([C:11]1[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=1)([C:4]1[CH:5]=[CH:6][C:7]([OH:10])=[CH:8][CH:9]=1)[CH3:3].C1([O:24][P:25](Cl)(Cl)=[O:26])C=CC=CC=1.[Cl-].[Al+3].[Cl-].[Cl-].[OH-:33].[K+].C1([OH:41])C=CC=CC=1>C(Cl)Cl.CO>[CH3:3][C:2]([C:4]1[CH:5]=[CH:6][C:7]([OH:10])=[CH:8][CH:9]=1)([C:11]1[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=1)[CH3:1].[P:25]([O-:26])([O-:41])([O-:24])=[O:33]

Participants

8

Reactant 5

HCID 996PhenolHCID 6623Bisphenol AHCID 13038Phosphorodichloridic acid, phenyl esterHCID 14797Potassium HydroxideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 86591309BPA phosphate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
120 °C

Procedure

97.49 g (0.43 mol) of BPA, 100.00 g (0.47 mol) of phenyldichlorophosphate, and 0.89 g (6.66 mmol) of aluminum chloride were taken in a reaction kettle. The kettle was fitted with an overhead stirrer, a water condenser with nitrogen outlet and a nitrogen inlet. The nitrogen outlet was immersed in a beaker containing KOH solution to absorb the evolved HCl. The reaction mixture was stirred-at 90° C. for 2 h and further at 120° C. for 4 h. A sample of the reaction mixture was drawn and 31P NMR was done to show that there was no phenyldichlorophosphate left and the conversion was nearly 75%. To the reaction mixture 26.06 g (0.28 mol) of phenol was added and the temperature was increased to 140° C. and the reaction mixture was stirred at that temperature for 3 h. After confirming from the 31P NMR spectrum that there was no reactive P—Cl bonds, the reaction mixture was cooled down to room temperature and dissolved in minimum amount of methylene chloride. The methylene chloride solution was added slowly into an excess amount of methanol. The methanol solution was decanted and the precipitate was again dissolved in a minimum amount of methylene chloride and poured into excess methanol. After decanting the methanol solution the precipitate was dried in a vacuum oven at 60-80° C. for 6 h to give 135 g (yield, ˜87%) of the desired solid poly(BPA-phosphate).

Workup

  1. customThe kettle was fitted with an overhead stirrer, a water condenser with nitrogen outlet and a nitrogen inlet
  2. customto absorb the evolved HCl
  3. waitleft
  4. temperaturethe temperature was increased to 140° C.
  5. stirringthe reaction mixture was stirred at that temperature for 3 h
  6. temperaturethe reaction mixture was cooled down to room temperature
  7. customThe methanol solution was decanted
  8. dissolutionthe precipitate was again dissolved in a minimum amount of methylene chloride
  9. additionpoured into excess methanol
  10. customAfter decanting the methanol solution the precipitate
  11. customwas dried in a vacuum oven at 60-80° C. for 6 h
  12. customto give

Sources & evidence

ORD record
ord-4d24c050fa76405b92ea9ef4809f20d5
Source dataset
uspto-grants-2004_03
Patent number
US06713598B2

Linked notes

Loading…