Diethyl Oxalate → HCID 178519132, compound

HRID 1612796Notes

Reaction equation

HRID 1612796 reaction equation
[F:1][C:2]1[C:3]([OH:11])=[C:4]([C:8](=[O:10])[CH3:9])[CH:5]=[CH:6][CH:7]=1.[C:12](OCC)(=[O:18])[C:13]([O:15][CH2:16]C)=[O:14].[O-]CC.[Na+]>C(O)C>[F:1][C:2]1[C:3]([OH:11])=[C:4]([C:8]([C:9]2[CH2:16][O:15][C:13](=[O:14])[C:12]=2[OH:18])=[O:10])[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 2723922Sodium ethoxideHCID 107731763'-Fluoro-2'-hydroxyacetophenone

Product 1

HCID 178519132HCID 178519132, compoundYield 40.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A solution of 1-(3-fluoro-2-hydroxyphenyl) ethanone (30 g) and diethyl oxalate (31 g) in ethanol (600 mls) was added dropwise to sodium ethoxide (from 9.85 g of sodium) in ethanol (600 mls) and the mixture was stirred and heated at reflux for 2 days. The mixture was cooled, diluted with 60-80 petrol and the solid was collected and dried. A suspension of the product in water (1.2 l) was stirred with formaldehyde (24 mls of 37%) for 1.5 hours. The solid was filtered out, the filtrate was washed with ether, and traces of ether were removed by evaporation under vacuum. The aqueous solution was acidified to pH3, the precipitate was collected, washed with water and recrystallised from acetone/water to give the title compound as yellow needles (18.7 g). M.p. 194°-208° (decomp), i.r. λmax (nujol) 1768, 1642 cm-1 (C=O).

Workup

  1. temperatureheated
  2. temperatureat reflux for 2 days
  3. temperatureThe mixture was cooled
  4. customthe solid was collected
  5. customdried
  6. additionA suspension of the product in water (1.2 l)
  7. stirringwas stirred with formaldehyde (24 mls of 37%) for 1.5 hours
  8. filtrationThe solid was filtered out
  9. washthe filtrate was washed with ether, and traces of ether
  10. customwere removed by evaporation under vacuum
  11. customthe precipitate was collected
  12. washwashed with water
  13. customrecrystallised from acetone/water

Sources & evidence

ORD record
ord-a38a189fbcb042b6b61f42f7020552ac
Source dataset
uspto-grants-1993_03
Patent number
US05190967

Reaction notes

Loading…