Triethylamine → 3-Acetyl-6-bromo-4-phenylisochromen-1-one

HRID 750310Notes

Reaction equation

HRID 750310 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:10](=[CH:11][CH:12]=1)[C:8](=[O:9])[O:7][C:6]([C:13](O)=[O:14])=[C:5]2[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[CH3:22]C1(C)OC(=O)CC(=O)O1.C(N(CC)CC)C.C(N=C=NCCCN(C)C)C>CN(C)C1C=CN=CC=1.ClCCl>[C:13]([C:6]1[O:7][C:8](=[O:9])[C:10]2[C:4]([C:5]=1[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)=[CH:3][C:2]([Br:1])=[CH:12][CH:11]=2)(=[O:14])[CH3:22]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 230607776-Bromo-4-phenyl-3-isocoumarincarboxylic acid

Product 1

HCID 230605293-Acetyl-6-bromo-4-phenylisochromen-1-oneYield 81%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

[Step 1] To a solution of 6-bromo-4-phenyl-3-isocoumarincarboxylic acid (10.3 g), 2,2-dimethyl-[1,3]dioxane-4,6-dione (4.76 g), dimethylpyridin-4-yl-amine (5.50 g) and triethylamine (6.3 ml) in dichloromethane (100 ml) was added 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (8.6 g) at room temperature and the mixture was stirred at room temperature for 15 hrs. The mixture was diluted with dichloromethane, washed with 1N hydrochloric acid and saturated brine and dried by adding sodium sulfate. The solvent was evaporated under reduced pressure and the obtained residue dissolved in water (200 ml) and acetic acid (100 ml) and the mixture was heated under reflux for 10 hrs. The solvent was evaporated under reduced pressure, water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated sodium hydrogen carbonate solution and saturated brine and dried by adding sodium sulfate. The obtained residue was crystallized from diisopropyl ether to give 3-acetyl-6-bromo-4-phenyl-isochromen-1-one (8.29 g, 81%).

Workup

  1. washwashed with 1N hydrochloric acid and saturated brine
  2. customdried
  3. additionby adding sodium sulfate
  4. customThe solvent was evaporated under reduced pressure
  5. dissolutionthe obtained residue dissolved in water (200 ml)
  6. temperatureacetic acid (100 ml) and the mixture was heated
  7. temperatureunder reflux for 10 hrs
  8. customThe solvent was evaporated under reduced pressure, water
  9. additionwas added
  10. extractionthe mixture was extracted with ethyl acetate
  11. washThe extract was washed with saturated sodium hydrogen carbonate solution and saturated brine
  12. customdried
  13. additionby adding sodium sulfate
  14. customThe obtained residue was crystallized from diisopropyl ether

Sources & evidence

ORD record
ord-6739db076a08442ca6e3d8892bfc2744
Source dataset
uspto-grants-2008_07
Patent number
US07402595B2

Reaction notes

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