Diethyl Oxalate → HCID 54202444, compound

HRID 1606820Notes

Reaction equation

HRID 1606820 reaction equation
[C:1]([C:4]1[C:22](O)=[CH:21][CH:20]=[CH:19][C:5]=1[O:6][CH2:7][CH:8]([OH:18])[CH2:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=1)(=[O:3])C.[O-][CH2:25][CH3:26].[Na+].[Na].C(OCC)(=O)C(OCC)=[O:31]>CCOCC.C(O)C.Cl>[C:1]([C:4]1[CH:22]=[CH:21][CH:20]=[CH:19][C:5]=1[O:6][CH2:7][CH:8]([OH:18])[CH2:9][O:10][C:11]1[CH:12]=[CH:13][C:14]([F:17])=[CH:15][CH:16]=1)([O:3][CH2:25][CH3:26])=[O:31]

Participants

8

Reactant 4

HCID 7268Diethyl OxalateHCID 2723922Sodium ethoxideHCID 5360545SodiumHCID 21544804HCID 21544804, compound

Product 1

HCID 54202444HCID 54202444, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 702EthanolSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

A suspension of 1-(2-acetyl-3-hydroxyphenoxy)-2-hydroxy-3 -(p-fluorophenoxy) propane (25.6 g) in diethyl oxalate (30 ml) was added to a suspension of sodium ethoxide, prepared from sodium (6.0 g) and ethanol (60 ml) in dry ether (400 ml). The mixture was then heated under reflux for 2 hours, cooled, and poured onto ice (200 g). After acidification with a solution of acetic acid (24 ml) in water (160 ml), the ethereal layer was separated, and the aqueous layer was extracted with ether (3 × 50 ml). The organic extracts were combined and concentrated under reduced pressure to give yellow oil. This was dissolved in ethanol (100 ml) containing hydrochloric acid (10 drops) and the solution heated under reflux for 1 hour. After removal of the solvent under reduced pressure the yellow residue was crystallized from ethanol to give 1-(2-carbethoxy-phenoxy)-2-hydroxy-3-(p-fluorophenoxy) propane (22.0 g) as cream crystals, m.p. 112°-114° C.

Workup

  1. temperatureThe mixture was then heated
  2. temperatureunder reflux for 2 hours
  3. temperaturecooled
  4. additionpoured onto ice (200 g)
  5. customAfter acidification with a solution of acetic acid (24 ml) in water (160 ml), the ethereal layer was separated
  6. extractionthe aqueous layer was extracted with ether (3 × 50 ml)
  7. concentrationconcentrated under reduced pressure
  8. customto give yellow oil
  9. temperaturethe solution heated
  10. temperatureunder reflux for 1 hour
  11. customAfter removal of the solvent under reduced pressure the yellow residue
  12. customwas crystallized from ethanol

Sources & evidence

ORD record
ord-9dbf73ee24a848ab89052306d569ddee
Source dataset
uspto-grants-1976_04
Patent number
US03953604

Reaction notes

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