Hydrogen Peroxide → 3-(2-Hydroxyethyl)-1-{4-nitro-2-[(1E)-prop-1-en-1-yl]phenyl}pyridin-2(1H)-one

HRID 452236Notes

Reaction equation

HRID 452236 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]2[CH:15]=[CH:14][CH:13]=[C:12]([CH:16]=[CH2:17])[C:11]2=[O:18])=[C:6](/[CH:19]=[CH:20]/[CH3:21])[CH:5]=1)([O-:3])=[O:2].C12BC(CCC1)CCC2.[OH-:31].[Na+].OO>O1CCCC1>[OH:31][CH2:17][CH2:16][C:12]1[C:11](=[O:18])[N:10]([C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=2/[CH:19]=[CH:20]/[CH3:21])[CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 595366061-{4-Nitro-2-[(1E)-prop-1-en-1-yl]phenyl}-3-vinylpyridin-2(1H)-one

Product 1

HCID 595366073-(2-Hydroxyethyl)-1-{4-nitro-2-[(1E)-prop-1-en-1-yl]phenyl}pyridin-2(1H)-one

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

452 g (1.60 mmol) of the compound from Example 45A are dissolved in 1.7 ml of anhydrous tetrahydrofuran and cooled to 0° C. 488 mg (176 mmol) of 9-bora-bicyclo[3.3.1]nonane (0.5 M solution in tetrahydrofuran) are added slowly, and the mixture is stirred at room temperature for 2 h. The mixture is then again cooled to 0° C., and 8 ml of 1N aqueous sodium hydroxide solution are added slowly. After the addition has ended, 1.6 ml of 30% strength hydrogen peroxide solution are added dropwise at this temperature. The mixture is stirred at 0° C. for 30 min and then washed with 1.3 ml of 40% strength sodium bisulphite solution to destroy the peroxides and diluted with 500 ml of ethyl acetate. The organic phase is removed and the aqueous phase is extracted twice with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulphate and, after filtration, concentrated to dryness under reduced pressure. The product is purified by chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate=2:1). This gives 514 mg (100% of theory) of the desired product.

Workup

  1. temperatureThe mixture is then again cooled to 0° C.
  2. additionAfter the addition
  3. stirringThe mixture is stirred at 0° C. for 30 min
  4. washwashed with 1.3 ml of 40% strength sodium bisulphite solution
  5. customto destroy the peroxides
  6. additiondiluted with 500 ml of ethyl acetate
  7. customThe organic phase is removed
  8. extractionthe aqueous phase is extracted twice with ethyl acetate
  9. washThe combined organic phases are washed with saturated sodium chloride solution
  10. dry with materialdried over sodium sulphate
  11. filtrationafter filtration
  12. concentrationconcentrated to dryness under reduced pressure
  13. customThe product is purified by chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate=2:1)

Sources & evidence

ORD record
ord-41b3ebcb6fce4a8e9b1c8c8c5caced27
Source dataset
uspto-grants-2013_07
Patent number
US08487111B2

Reaction notes

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