Hydrogen Peroxide → Methyl 7-(2,2-dimethylpropionylamino)-3-hydroxychroman-8-carboxylate

HRID 2200342Notes

Reaction equation

HRID 2200342 reaction equation
[CH3:1][C:2]([CH3:21])([CH3:20])[C:3]([NH:5][C:6]1[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:9]([CH:10]=[CH:11][CH2:12][O:13]2)=[CH:8][CH:7]=1)=[O:4].[OH-:22].[Na+].OO>C1COCC1.C(OCC)(=O)C.O>[CH3:1][C:2]([CH3:21])([CH3:20])[C:3]([NH:5][C:6]1[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:9]([CH2:10][CH:11]([OH:22])[CH2:12][O:13]2)=[CH:8][CH:7]=1)=[O:4]

Participants

7

Reactant 3

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 70983794Methyl 7-pivalamido-2H-chromene-8-carboxylate2×

Product 1

HCID 89705247Methyl 7-(2,2-dimethylpropionylamino)-3-hydroxychroman-8-carboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of borane dimethyl sulphide complex (7.38 mL) was added to an ice cooled, stirred solution of methyl 7-(2,2-dimethylpropionylamino)-2H-chromene-8-carboxylate (Intermediate 12, 7.49 g) in anhydrous THF (100 mL) and the mixture was stirred at room temperature for two hours. The resulting mixture was cooled in an ice bath and water (2.6 mL) was added carefully followed successively by 3M sodium hydroxide (31 mL) and 50% hydrogen peroxide (16 mL). After stirring vigorously at room temperature for 45 minutes, the mixture was diluted with ethyl acetate and water and the layers were separated. The organic layer was washed with brine, dried (Na2SO4) and filtered. The filtrate was evaporated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 10-60% to give methyl 7-(2,2-dimethylpropionylamino)-3-hydroxychroman-8-carboxylate (3.46 g) as a white foam.

Workup

  1. temperaturecooled
  2. temperatureThe resulting mixture was cooled in an ice bath
  3. stirringAfter stirring vigorously at room temperature for 45 minutes
  4. customthe layers were separated
  5. washThe organic layer was washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customThe filtrate was evaporated in vacuo
  9. customthe residue was purified by chromatography on silica
  10. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 10-60%

Sources & evidence

ORD record
ord-4a7e90c70ebb42668c511afb96023c36
Source dataset
uspto-grants-2016_06
Patent number
US09359369B2

Reaction notes

Loading…