Diethyl Malonate → HCID 22267218, compound

HRID 488862Notes

Reaction equation

HRID 488862 reaction equation
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([C:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=O)=[C:4]([OH:17])[CH:3]=1.[C:18](OCC)(=[O:25])[CH2:19][C:20]([O:22]CC)=[O:21].C1CCN2C(=NCCC2)CC1>C(OCC)(=O)C>[Cl:8][C:7]1[CH:6]=[C:5]2[C:4](=[CH:3][C:2]=1[Cl:1])[O:17][C:18](=[O:25])[C:19]([C:20]([OH:22])=[O:21])=[C:9]2[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 13284266HCID 13284266, compound

Product 1

HCID 22267218HCID 22267218, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
170 °C

Procedure

A mixture of (4,5-dichloro-2-hydroxyphenyl) (phenyl)methanone (1.5 g), diethyl malonate (1.28 ml) and DBU (0.25 ml) was stirred at 170° C. for 30 minutes. The reaction mixture was dissolved in ethyl acetate (50 ml), and washed with water followed by a 1 N solution of hydrochloric acid and a saturated aqueous solution of sodium chloride. After drying over magnesium sulfate, the solvent was distilled off under reduced presurre, and the residue was purified by a column chromatography (packing: silica gel, eluent: ethyl acetate-hexane=1:9). The resultant crude product of ethyl 6,7-dichloro-2-oxo-4-phenyl-2H-chromene-3-carboxylate was dissolved in acetic acid (10 ml) and concentrated hydrochloric acid (5 ml), and heated under reflux for 1 hour. The reaction solution was concentrated under reduced pressure, and the resultant residue was dissolved in a solvent mixture of THF (10 ml) and ethyl acetate (50 ml), and then washed with water followed by a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by recrystallization from ethyl acetate to obtain the title compound (0.65 g, yield: 34%).

Workup

  1. washwashed with water
  2. dry with materialAfter drying over magnesium sulfate
  3. distillationthe solvent was distilled off
  4. customthe residue was purified by a column chromatography (packing: silica gel, eluent: ethyl acetate-hexane=1:9)
  5. dissolutionThe resultant crude product of ethyl 6,7-dichloro-2-oxo-4-phenyl-2H-chromene-3-carboxylate was dissolved in acetic acid (10 ml)
  6. temperatureconcentrated hydrochloric acid (5 ml), and heated
  7. temperatureunder reflux for 1 hour
  8. concentrationThe reaction solution was concentrated under reduced pressure
  9. dissolutionthe resultant residue was dissolved in a solvent mixture of THF (10 ml) and ethyl acetate (50 ml)
  10. washwashed with water
  11. dry with materialAfter drying over magnesium sulfate
  12. distillationthe solvent was distilled off under reduced pressure
  13. customthe residue was purified by recrystallization from ethyl acetate

Sources & evidence

ORD record
ord-05ed6e3d55a24a92889e5ba1ffaddc7d
Source dataset
uspto-grants-2005_12
Patent number
US06974806B2

Reaction notes

Loading…