Ethyl formate → 7-methylsulfonylamino-6-phenoxy-4H-1-benzopyran-4-one

HRID 1031675Notes

Reaction equation

HRID 1031675 reaction equation
[OH:1][C:2]1[CH:7]=[C:6]([NH:8][S:9]([CH3:12])(=[O:11])=[O:10])[C:5]([O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:4][C:3]=1[C:20]([CH3:22])=[O:21].[CH:23](OCC)=O.[H-].[Na+]>C1(C)C=CC=CC=1>[CH3:12][S:9]([NH:8][C:6]1[C:5]([O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:4][C:3]2[C:20](=[O:21])[CH:22]=[CH:23][O:1][C:2]=2[CH:7]=1)(=[O:11])=[O:10]

Participants

5

Reactant 3

HCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 10734538HCID 10734538, compound

Product 1

HCID 106164807-methylsulfonylamino-6-phenoxy-4H-1-benzopyran-4-oneYield 65%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In 70 ml of toluene was suspended 3.4 g of methyl 2-hydroxy-4-methylsulfonylamino-5-phenoxyphenyl ketone. 17 ml of ethyl formate was added thereto. Further, 3.4 g of sodium hydride (purity: 60%) was added thereto in portions in 20 minutes. The mixture was refluxed for 5 hours. The reaction mixture was introduced into 300 ml of ice water. The aqueous layer was separated and adjusted to pH 4 with 4N hydrochloric acid. The mixture was then extracted with two 100-ml portions of ethyl acetate. The extracts were combined and subjected to distillation under reduced pressure to remove the solvent. The residue was dissolved in 20 ml of acetic acid. 1 ml of concentrated hydrochloric acid was added. The mixture was heated for 30 minutes at 50°-60° C. 200 ml of water was added thereto. The resulting mixture was extracted with 200 ml of ethyl acetate. The extract was 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 recrystallized from acetonitrile to obtain 2.28 g (yield: 65%) of 7-methylsulfonylamino-6-phenoxy-4H-1-benzopyran-4-one having a melting point of 216.7°-217 6° C.

Workup

  1. temperatureThe mixture was refluxed for 5 hours
  2. customThe aqueous layer was separated
  3. extractionThe mixture was then extracted with two 100-ml portions of ethyl acetate
  4. distillationsubjected to distillation under reduced pressure
  5. customto remove the solvent
  6. dissolutionThe residue was dissolved in 20 ml of acetic acid
  7. addition1 ml of concentrated hydrochloric acid was added
  8. temperatureThe mixture was heated for 30 minutes at 50°-60° C
  9. addition200 ml of water was added
  10. extractionThe resulting mixture was extracted with 200 ml of ethyl acetate
  11. washThe extract was washed with water
  12. dry with materiala saturated aqueous sodium chloride solution in this order, and dried with anhydrous magnesium sulfate
  13. customThe solvent was removed by distillation under reduced pressure
  14. customThe residue was recrystallized from acetonitrile

Sources & evidence

ORD record
ord-02f4f2087738495c9022c641bf1d8962
Source dataset
uspto-grants-1990_09
Patent number
US04954518

Reaction notes

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