Diisopropyl Ether → HCID 22168218, compound

HRID 1031695Notes

Reaction equation

HRID 1031695 reaction equation
C([O:4][C:5]1[C:6]([NH:15][S:16]([CH3:19])(=[O:18])=[O:17])=[CH:7][C:8]([OH:14])=[C:9]([C:11]([CH3:13])=[O:12])[CH:10]=1)(=O)C.Cl(O)(=O)(=O)=O.[CH:25](OC(C)C)(C)C>C([O-])([O-])OCC>[OH:4][C:5]1[C:6]([NH:15][S:16]([CH3:19])(=[O:17])=[O:18])=[CH:7][C:8]2[O:14][CH:25]=[CH:13][C:11](=[O:12])[C:9]=2[CH:10]=1

Participants

5

Reactant 3

HCID 7914Diisopropyl EtherHCID 24247Perchloric AcidHCID 14722315HCID 14722315, compound

Product 1

HCID 22168218HCID 22168218, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 53630039EthylorthoformateSolvent

Procedure

2.0 g of methyl 5-acetoxy-2-hydroxy-4-methylsulfonylaminophenyl ketone was suspended in 14 ml of ethyl orthoformate. Thereto was dropwise added 2.0 g of 70% (w/w) perchloric acid in 10 minutes with ice-cooling. The mixture was stirred for 1.5 hours at 20°-25° C. The reaction mixture was mixed with 20 ml of diisopropyl ether. The resulting crystal was collected by filtration and mixed with 20 ml of water. The mixture was refluxed for 5 minutes and then cooled. 50 ml of ethyl acetate was added thereto. The organic layer was separated, washed with water and a saturated aqueous sodium chloride solution in this order, and dried with anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure. The residue was dissolved in 14 ml of a 1N aqueous sodium hydroxide solution. The mixture was stirred for 30 minutes at 20°-25° C. The reaction mixture was adjusted to pH 2 with 6N hydrochloric acid. The resulting crystal was collected by filtration and recrystallized from a mixed solvent of N,N-dimethylformamide and water to obtain 1.0 g (yield: 59%) of 6-hydroxy-7-methylsulfonylamino-4H-1-benzopyran-4-one having a melting point of >250° C.

Workup

  1. customin 10 minutes
  2. temperaturecooling
  3. filtrationThe resulting crystal was collected by filtration
  4. additionmixed with 20 ml of water
  5. temperatureThe mixture was refluxed for 5 minutes
  6. temperaturecooled
  7. addition50 ml of ethyl acetate was added
  8. customThe organic layer was separated
  9. washwashed with water
  10. dry with materiala saturated aqueous sodium chloride solution in this order, and dried with anhydrous magnesium sulfate
  11. customThe solvent was removed by distillation under reduced pressure
  12. dissolutionThe residue was dissolved in 14 ml of a 1N aqueous sodium hydroxide solution
  13. stirringThe mixture was stirred for 30 minutes at 20°-25° C
  14. filtrationThe resulting crystal was collected by filtration
  15. customrecrystallized from a mixed solvent of N,N-dimethylformamide and water

Sources & evidence

ORD record
ord-24ed6b7f0ac24abc926761c187d6b944
Source dataset
uspto-grants-1990_09
Patent number
US04954518

Reaction notes

Loading…