Phenol → Allyl phenyl carbonate

HRID 1742473Notes

Reaction equation

HRID 1742473 reaction equation
[CH2:1]([OH:4])[CH:2]=[CH2:3].Cl[C:6]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:7].N1C=CC=CC=1.NN.C(=O)([O-])[O-].C(OCC=C)(=O)NN.C1(O)C=CC=CC=1>C(Cl)Cl>[C:6](=[O:7])([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[O:4][CH2:1][CH:2]=[CH2:3]

Participants

9

Reactant 7

HCID 996PhenolHCID 1049PyridineHCID 7858Allyl AlcoholHCID 9321HydrazineHCID 15891Phenyl chloroformateHCID 19660Carbonate IonHCID 11137137Hydrazinecarboxylic acid, 2-propenyl ester

Product 1

HCID 11412694Allyl phenyl carbonateYield 97%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Allyl phenyl carbonate was prepared in 97% yield by reacting 17.6 grams (0.3 mole) of allyl alcohol with 48.4 grams (0.3 mole) of phenyl chloroformate in the presence of 26.4 grams (0.33 mole) of pyridine and 300 ml of methylene chloride. The allyl phenyl carbonate soluation was washed with 5% HCl, water, dried over anhydrous sodium sulfate, filtered and the methylene chloride evaporated on a rotating evaporator under reduced pressure. The residual allyl phenyl carbonate (52.7 grams--0.29 mole) was dissolved in 200 ml of methanol and treated with 16.0 grams (0.32 mole) of 64% aqueous hydrazine at room temperature. After two hours, gase chromatography indicated that the carbonate had been completely converted to allyl carbazate and phenol. The reaction mixture was stripped of volatiles on the rotating evaporator. The residue was taken up in 200 ml of methylene chloride and washed with 50 grams of 25% sodium hydroxide to remove the phenol. The methylene chloride layer was washed with saturated salt solution, dried over sodium sulfate, filtered and the methylene chloride stripped off on the rotating evaporator. The residue weighed 9.2 grams and assayed 98.0% by gas chromatography. An additional 3.9 grams was recovered by reextracting the aqueous wash.

Workup

  1. washThe allyl phenyl carbonate soluation was washed with 5% HCl, water
  2. dry with materialdried over anhydrous sodium sulfate
  3. filtrationfiltered
  4. customthe methylene chloride evaporated on a rotating evaporator under reduced pressure
  5. dissolutionThe residual allyl phenyl carbonate (52.7 grams--0.29 mole) was dissolved in 200 ml of methanol
  6. customThe reaction mixture was stripped of volatiles on the rotating evaporator
  7. washwashed with 50 grams of 25% sodium hydroxide
  8. customto remove the phenol
  9. washThe methylene chloride layer was washed with saturated salt solution
  10. dry with materialdried over sodium sulfate
  11. filtrationfiltered
  12. customthe methylene chloride stripped off on the rotating evaporator
  13. customAn additional 3.9 grams was recovered

Sources & evidence

ORD record
ord-d229863055854a8abd39f7eeb1b5ad94
Source dataset
uspto-grants-1994_08
Patent number
US05338853

Reaction notes

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