Phosgene → 9,9-bis(4-hydroxyphenyl) fluorene Bisphenol-A

HRID 35984

Reaction equation

HRID 35984 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:11]2[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][CH:12]=2)([CH3:10])[CH3:9])=[CH:4][CH:3]=1.[OH:18][C:19]1[CH:24]=[CH:23][C:22]([C:25]2([C:38]3[CH:43]=[CH:42][C:41]([OH:44])=[CH:40][CH:39]=3)[C:37]3[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=3[C:31]3[C:26]2=[CH:27][CH:28]=[CH:29][CH:30]=3)=[CH:21][CH:20]=1.C(C1C=CC(O)=CC=1)(C)(C)C.[OH-].[Na+].C(Cl)(Cl)=O>CN(C)C1C=CN=CC=1.C(Cl)Cl.O>[OH:18][C:19]1[CH:20]=[CH:21][C:22]([C:25]2([C:38]3[CH:39]=[CH:40][C:41]([OH:44])=[CH:42][CH:43]=3)[C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][C:31]=3[C:32]3[C:37]2=[CH:36][CH:35]=[CH:34][CH:33]=3)=[CH:23][CH:24]=1.[OH:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([C:11]2[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=2)([CH3:10])[CH3:9])=[CH:6][CH:7]=1

Participants

9

Reactant 5

HCID 6371PhosgeneHCID 6623Bisphenol AHCID 73934-tert-ButylphenolHCID 14798Sodium Hydroxide2×HCID 767169,9-Bis(4-hydroxyphenyl)fluorene

Product 1

HCID 1317189889,9-bis(4-hydroxyphenyl) fluorene Bisphenol-A

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a 100 mL high pressure reactor with plug are added Bisphenol-A (0.913 g, 4.0 mmole), 9,9-bis(4-hydroxyphenyl) fluorene (2.102 g, 6.0 mmole), p-tert-butyl-phenol (0.045 g, 0.30 mmole), 50 percent NaOH (2.0 g, 25.0 mmole) and water (16.14 g). The reactor plug is loosely screwed in, and a needle connected to a nitrogen source is then inserted through the injector port septum. Nitrogen gas is blown through the air space of the reactor for 10 minutes, then the plug is tightened down. The sealed reactor is placed in a water bath (69°-71° C.), and a magnetic stirrer is started. Within 15 minutes the monomer has dissolved. To this stirred mixture is added phosgene solution in methylene chloride (20.08 g of 6.65 percent solution, 13 mmole) by 25 mL gastight syringe. The syringe is removed and the reaction mixture shaken for 30 seconds. A second shot of 50 percent NaOH (2.0 g, 25 mmole) is added by syringe through the septum. The mixture is shaken 1 minute, then further methylene chloride (11.17 g) is added by syringe, followed by 4-dimethylamino pyridine (0.6 mL of a 1 percent aqueous solution). This mixture is shaken 1 minute, then the reactor swirled in an ice bath. The reactor is opened, and the aqueous phase pipetted off. The organic phase is washed once with 1N HCl and twice with water, and it is then evaporated on a petri dish to give a 9,9-bis(4-hydroxyphenyl) fluorene/Bisphenol-A copolycarbonate film.

Workup

  1. customThe sealed reactor is placed in a water bath
  2. custom(69°-71° C.), and a magnetic stirrer
  3. dissolutionWithin 15 minutes the monomer has dissolved
  4. customThe syringe is removed
  5. stirringThe mixture is shaken 1 minute
  6. stirringThis mixture is shaken 1 minute
  7. customthe reactor swirled in an ice bath
  8. washThe organic phase is washed once with 1N HCl and twice with water, and it
  9. customis then evaporated on a petri dish

Sources & evidence

ORD record
ord-8fbee8e91a374f089ae01b0faa24dbcb
Source dataset
uspto-grants-1995_05
Patent number
US05412064

Linked notes

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