Diethyl Oxalate → HCID 21544772, compound

HRID 1606795Notes

Reaction equation

HRID 1606795 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]([Br:17])=[CH:13][CH:12]=1)(=[O:3])[CH3:2].[C:24](OCC)(=O)[C:25]([O:27]CC)=[O:26].[O-]CC.[Na+]>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]([Br:17])=[CH:13][CH:12]=1)[CH:19]=[CH:20][CH:21]=2)([OH:27])=[O:26]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 2723922Sodium ethoxideHCID 539482751-[2-[3-(4-Bromophenoxy)-2-hydroxypropoxy]-6-hydroxyphenyl]ethanone

Product 1

HCID 21544772HCID 21544772, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A mixture of 1-(2-acetyl-3-hydroxyphenoxy)-2-hydroxy-3-p-bromophenoxypropane (15.2 g) and diethyl oxalate (15 ml) was added to a suspension of sodium ethoxide (prepared from 3.0 sodium) in absolute ether. The mixture was heated under reflux for 1.5 hours and then poured onto ice (100 g). After acidification with a solution of acetic acid (12 ml) in water (80 ml), the ether layer was separated and the aqueous layer was extracted with ether (3 × 25 ml). The combined ether solutions were evaporated and the residue was dissolved in a mixture of acetic acid (80 ml) and hydrochloric acid (30 ml) and heated under reflux for 1 hour. Recrystallization from acetic acid yielded crude 1-(2-carboxychromon-5-yloxy)-2-hydroxy-3-p-bromophenoxypropane, (14.7 g), as a white solid, m.p. 188°-190°, which was converted to the ethyl ester employing absolute ethyl alcohol and concentrated sulphuric acid as catalyst. 1-(2-carbethoxychromon-5-yloxy)-2-hydroxy-2-p-bromophenoxypropane was obtained as white crystals, m.p. 79°-80° after recrystallization from aqueous dioxane.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 1.5 hours
  3. additionpoured onto ice (100 g)
  4. customAfter acidification with a solution of acetic acid (12 ml) in water (80 ml), the ether layer was separated
  5. extractionthe aqueous layer was extracted with ether (3 × 25 ml)
  6. customThe combined ether solutions were evaporated
  7. dissolutionthe residue was dissolved in a mixture of acetic acid (80 ml) and hydrochloric acid (30 ml)
  8. temperatureheated
  9. temperatureunder reflux for 1 hour
  10. customRecrystallization from acetic acid

Sources & evidence

ORD record
ord-423705d3d196476e834bf0d9d68a648d
Source dataset
uspto-grants-1976_04
Patent number
US03953604

Reaction notes

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