Diethyl Oxalate → HCID 21544769, compound

HRID 1606797Notes

Reaction equation

HRID 1606797 reaction equation
[C:1]([C:4]1[C:22]([OH:23])=[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]([Cl:17])=[CH:13][CH:12]=1)(=[O:3])[CH3:2].[C:24](OCC)(=O)[C:25]([O:27]CC)=[O:26]>CCOCC>[C:25]([C:24]1[O:23][C:22]2[C:4]([C:1](=[O:3])[CH:2]=1)=[C:5]([O:6][CH2:7][CH:8]([OH:18])[CH2:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=1)[CH:19]=[CH:20][CH:21]=2)([OH:27])=[O:26]

Participants

4

Reactant 2

HCID 7268Diethyl OxalateHCID 54453763HCID 54453763, compound

Product 1

HCID 21544769HCID 21544769, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A mixture of 1-(2-acetyl-3-hydroxyphenoxy)-2-hydroxy-3-p-chlorophenoxypropane (13.5 g) and diethyl oxalate (15 ml) was added to a suspension of alcohol-free sodium ethoxide (prepared from sodium 3 g) in absolute ether (200 ml). The mixture was heated under reflux for 1.5 hours during which time a yellow solid separated. The reaction mixture was poured onto ice (100 g) and acidified with a solution of acetic acid (12 ml) in water (80 ml). The ether layer was separated and the aqueous layer extracted with ether (3 × 25 ml). The ether layer was combined with the ether extracts and the solvent was evaporated. Acetic acid (80 ml) and hydrochloric acid (30 ml) were added to the residue and the resulting solution was heated under reflux for 1 hour. On pouring into water a beige gum was precipitated which soon solidified and was filtered. Recrystallization from acetic acid gave crude 1-(2-carboxychromon-5-yloxy)-2-hydroxy-3-p-chlorophenoxypropane (12.0 g), as a white solid, m.p. 191°-193°. The impure acid (10 g) was heated under reflux for 5 hours with ethanol (100 ml) and concentrated sulphuric acid (10 drops). The solvent was then removed on a rotary evaporator; the residual oil was dissolved in chloroform and washed successively with sodium bicarbonate solution and water. The solvent was removed and a small volume of ether was added to the residual oil which slowly crystallized to give a white solid (8.4 g), m.p. 98°-100°. Recrystallization from aqueous ethanol gave 1-(2-carboxychromon-5-yloxy)-2-hydroxy-3-p-chlorophenoxypropane (6.6 g) as white fluffy needles, m.p. 98°-100° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 1.5 hours during which time a yellow solid
  3. customseparated
  4. additionThe reaction mixture was poured onto ice (100 g)
  5. customThe ether layer was separated
  6. extractionthe aqueous layer extracted with ether (3 × 25 ml)
  7. customthe solvent was evaporated
  8. additionAcetic acid (80 ml) and hydrochloric acid (30 ml) were added to the residue
  9. temperaturethe resulting solution was heated
  10. temperatureunder reflux for 1 hour
  11. additionOn pouring into water a beige gum
  12. customwas precipitated which
  13. filtrationwas filtered
  14. customRecrystallization from acetic acid

Sources & evidence

ORD record
ord-88bb9d4a3cc94b5b8c14db4814defb3c
Source dataset
uspto-grants-1976_04
Patent number
US03953604

Reaction notes

Loading…