Hydrochloric Acid → (R)-5-phenyl-2-oxazolidinone

HRID 2186495Notes

Reaction equation

HRID 2186495 reaction equation
[OH:1][C@H:2]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH2:3]C(NN)=O.Cl.C([O:18][CH2:19]C)(=O)C.[N:21]([O-])=O.[Na+]>O.CO>[C:8]1([C@H:2]2[O:1][C:19](=[O:18])[NH:21][CH2:3]2)[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 23668193Sodium NitriteHCID 53854485HCID 53854485, compound

Product 1

HCID 11615228(R)-5-phenyl-2-oxazolidinoneYield 83%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent3×

Conditions

Temperature
5 °C

Procedure

In a 1 liter four-necked flask were put 150 g (0.83 mol) of (S)-3-hydroxy-3-phenylpropionohydrazide (optical purity: >99.9%e.e.), 150 g (1.44 mol) of 35% concentrated hydrochloric acid, 220 ml of water, and 100 ml of ethyl acetate. After cooling to 5° C., a solution of 57.5 g (0.83 mol) of sodium nitrite in 80 ml of water was added thereto dropwise at 5° C. over a 1 hour period, followed by stirring at that temperature for 30 minutes. The aqueous layer of the reaction mixture was extracted with 100 ml of ethyl acetate, and the extract was combined with the ethyl acetate layer of the reaction mixture. The combined ethyl acetate extract was washed twice with a 5% sodium chloride aqueous solution. The ethyl acetate layer was added dropwise to 100 ml of hot water at 100° C. thereby to conduct thermal decomposition and to recover the ethyl acetate. After the addition, the residue was cooled to room temperature, 200 ml of ethyl acetate added, and the mixture dried over anhydrous sodium sulfate. The solvent was evaporated to give 123.5 g of a crude product, which was dissolved in a mixed solvent of 150 ml of water and 90 ml of methanol. The solution was cooled to 5° C. to yield crystals of (R)-5-phenyl-2-oxazolidinone (113.1 g, 83%). Melting point: 96.4° C. Optical purity: >99.9%e.e..

Workup

  1. customIn a 1 liter four-necked flask were put
  2. extractionThe aqueous layer of the reaction mixture was extracted with 100 ml of ethyl acetate
  3. extractionThe combined ethyl acetate extract
  4. washwas washed twice with a 5% sodium chloride aqueous solution
  5. additionThe ethyl acetate layer was added dropwise to 100 ml of hot water at 100° C.
  6. customto recover the ethyl acetate
  7. additionAfter the addition
  8. temperaturethe residue was cooled to room temperature
  9. addition200 ml of ethyl acetate added
  10. dry with materialthe mixture dried over anhydrous sodium sulfate
  11. customThe solvent was evaporated
  12. customto give 123.5 g of a crude product, which
  13. temperatureThe solution was cooled to 5° C.

Sources & evidence

ORD record
ord-da738ff88983449b93a610c7bde06ea1
Source dataset
uspto-grants-2002_06
Patent number
US06403804B1

Reaction notes

Loading…