Carbon Dioxide → Diphenyl carbonate

HRID 654576Notes

Reaction equation

HRID 654576 reaction equation
[C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:8]1([O:14][C:15]2C=CC=CC=2)[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C(=O)=[O:22].O=O.[C]=O>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C([O-])(=O)C.[Co+2].C1(=O)C=CC(=O)C=C1>[C:15](=[O:22])([O:14][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[O:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

10

Reactant 5

HCID 280Carbon Dioxide2×HCID 977Oxygen2×HCID 996PhenolHCID 7583Diphenyl EtherHCID 178418416HCID 178418416, compound2×

Product 1

HCID 7597Diphenyl carbonateYield 305.9%

Reagents, catalysts & solvents 4

HCID 4650QuinoneCatalystHCID 6277Cobalt diacetateCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
100 °C

Procedure

There was added to a Parr stirred pressure reactor, 76.06 grams of phenol, 1.896 grams of diphenyl ether, 0.33 gram benzoquinone, 0.042 gram palladium diacetate, 0.035 gram of anhydrous cobalt diacetate, and 2.49 grams of tetrabutylammonium bromide. The reactor vessel was sealed, purged 4 times with CO2 at 400 psi and then charged with 0.278 mole of carbon dioxide, 0.209 mole of oxygen and 0.417 mole of carbon monoxide at room temperature. The resulting partial pressures of carbon dioxide were 400 psi, oxygen 300 psi, and carbon monoxide 600 psi. The mixture was heated to 100° C. while it was stirred rapidly to ensure efficient aeration of the solution phase. After 2 hours, 7.3 grams of diphenyl carbonate (8.4% yield based on phenol) had been produced. A total internal pressure drop of 195 psi was also observed during the first 2 hours. The reactor was exhausted to 1000 psi and then recharged with 300 psi of oxygen and 620 psi of carbon monoxide. An aliquot of the mixture was removed after 3 hours following the initiation of the reaction and it was found that 9.25 grams of diphenyl carbonate (10.7% yield) had formed based on GC. At the termination of the reaction which lasted 5 hours, a total of 13.2 grams of diphenyl carbonate (15.2% yield) had been formed. Recovery of the diphenyl carbonate is readily achieved by stripping the mixture to dryness at about 19 torr and 150°-190° C. followed by distillation at about 15 torr and 200° C.

Workup

  1. additionThere was added to a Parr
  2. customThe reactor vessel was sealed
  3. custompurged 4 times with CO2 at 400 psi
  4. stirringwas stirred rapidly

Sources & evidence

ORD record
ord-bc8731aac8b24b9ab77b156927a9fa72
Source dataset
uspto-grants-1992_07
Patent number
US05132447

Reaction notes

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