Phenylacetyl chloride → Phenylacetic Acid

HRID 1979624Notes

Reaction equation

HRID 1979624 reaction equation
[C:1]1([CH2:7][C:8](Cl)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-:11].[Ca+2].[OH-].[O:14]1[CH2:18]CCC1>O>[C:1]1([CH2:7][C:8](=[O:9])[C:18]([OH:14])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:1]1([CH2:7][C:8]([OH:9])=[O:14])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 7679Phenylacetyl chlorideHCID 8028TetrahydrofuranHCID 6093208Calcium Hydroxide

Product 2

HCID 997Phenylpyruvic acidYield 20.3%HCID 999Phenylacetic AcidYield 71.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

A 20 mL aliquot of 4.0 mmoles of potassium tricarbonyl [triphenylphosphine] cobaltate was charged to a 100 mL three-neck round bottom flask under nitrogen and cooled to 5° C. Phenylacetyl chloride (0.53 mL; 4 mmoles) was added to the flask, and the resultant solution containing the preformed cobaltate complex was charged into a 300 mL autoclave by means of a transfer needle under nitrogen. The autoclave had previously been charged with 16 mmoles (1.18 g) of calcium hydroxide as a suspension in 25 mLs tetrahydrofuran and 5 mLs water. The vessel was sealed, flushed with carbon monoxide, pressurized to 900 psig and heated to 50° C. for nine hours. The autoclave was vented and the contents were poured into a 250 mL separatory funnel. The reaction mixture was acidified with 10% hydrochloric acid and then treated with an excess of iodine. The organic phase was diluted with 100 mLs of diethyl ether and the lower aqueous phase was discarded. The organic phase was washed with saturated sodium thiosulfate until the color of iodine was dispelled. The resultant light yellow diethyl ether phase was washed with 10% sodium hydroxide (3×25 mLs) and the organic phase discarded. Acidification of the combined aqueous sodium hydroxide solution followed by re-extraction with diethyl ether (2×75 mLs) gave a clear solution. The solution was dried over MgSO4 and evaporated to give (0.81 mmoles; 20.3% yield) of phenylpyruvic acid and 2.84 mmoles (71.1% yield) of phenylacetic acid as identified by mass spectroscopy and comparison to an authentic sample.

Workup

  1. additionwas charged into a 300 mL autoclave by means of a transfer needle under nitrogen
  2. customThe vessel was sealed
  3. customflushed with carbon monoxide
  4. temperatureheated to 50° C. for nine hours
  5. additionthe contents were poured into a 250 mL separatory funnel
  6. additiontreated with an excess of iodine
  7. additionThe organic phase was diluted with 100 mLs of diethyl ether
  8. washThe organic phase was washed with saturated sodium thiosulfate until the color of iodine
  9. washThe resultant light yellow diethyl ether phase was washed with 10% sodium hydroxide (3×25 mLs)
  10. extractionAcidification of the combined aqueous sodium hydroxide solution followed by re-extraction with diethyl ether (2×75 mLs)
  11. customgave a clear solution
  12. dry with materialThe solution was dried over MgSO4
  13. customevaporated

Sources & evidence

ORD record
ord-1ba89701ee65437fa9896fc4537e952b
Source dataset
uspto-grants-1984_11
Patent number
US04481369

Reaction notes

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