Carbon Dioxide → Diphenyl carbonate

HRID 847531Notes

Reaction equation

HRID 847531 reaction equation
[C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:8]([C:12]([CH3:14])=[O:13])[CH:9]([CH3:11])C.[CH3:15][O:16]CCOCCOC.[C:24](=O)=O.O=O.[C]=O>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].C([O-])(=O)C.C([O-])(=O)C.[Co+2]>[C:15](=[O:16])([O:13][C:12]1[CH:8]=[CH:9][CH:11]=[CH:24][CH:14]=1)[O:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

9

Reactant 6

HCID 280Carbon DioxideHCID 977OxygenHCID 996PhenolHCID 7909Methyl Isobutyl KetoneHCID 8150DiglymeHCID 178418416HCID 178418416, compound

Product 1

HCID 7597Diphenyl carbonateYield 11.41%

Reagents, catalysts & solvents 2

HCID 6277Cobalt diacetateCatalystHCID 74236Tetrabutylammonium BromideCatalyst

Conditions

Temperature
100 °C

Procedure

There is introduced into an autoclave, 35.0 g (0.372 mol) of phenol, 1.14 g (3.54 mmol) of TBAB, 0.028 g (0.125 mmol) of Pd(OA)2, 0.018 g (0.102 mmol) of Co(OAc)2, 2.00 g (19.97 mmol) methyl isobutyl ketone (MIBK) and 35 g (261 mmol) of 2-methoxyethyl ether (diglyme). The reactor is sealed, charged with 900 psi CO2, leak-checked, and then exhausted to atmospheric pressure. The reactor is flushed 2×1500 psi CO followed by pressurization to 2100 psi with CO (high pressure leak test) before exhausting the reactor back to atmosphere pressure. The reactor is flushed with 4×1500 psi of O2 and at the end of the fourth oxygen purge cycle, the oxygen atmosphere in the reactor is reduced to 300 psig. There is added to the oxygen atmosphere, 400 psi of CO2 and 900 psi of CO. The reactor is heated to 100° C. Aliquots of the mixture are taken at predetermined times to determine the amount of diphenyl carbonate which has been produced. After each sampling, the reactor atmosphere is rejuvenated by exhausting the atmosphere to 1000 psi (Pt) followed by the addition of 200 psi of oxygen and 700 psi of carbon monoxide. After 5 hours of reaction there is obtained an 11.41% yield of a red-brown diphenyl carbonate. The reaction solution is distilled at 95-110° C. at 15 torr to effect the removal of phenol. The residue is then distilled at 155-165° C. at 15 torr to effect the recovery of diphenyl carbonate. There is obtained 6-10% yield of substantially white diphenyl carbonate. Following the procedure of example 1, active metallic catalyst values are recovered from the distillate residue.

Workup

  1. customThe reactor is sealed
  2. customThe reactor is flushed 2×1500 psi CO
  3. customThe reactor is flushed with 4×1500 psi of O2 and at the end of the fourth oxygen
  4. custompurge cycle
  5. additionThere is added to the oxygen atmosphere, 400 psi of CO2 and 900 psi of CO
  6. customhas been produced
  7. customAfter 5 hours of reaction

Sources & evidence

ORD record
ord-5afcae1ba1ce47ee9416338876321ffe
Source dataset
uspto-grants-1992_08
Patent number
US05142086

Reaction notes

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