Hydrogen Peroxide → HCID 66817774, compound

HRID 1754907Notes

Reaction equation

HRID 1754907 reaction equation
[OH-:1].[Na+].OO.[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][C:15]([C:32]#[N:33])([NH:18][C:19]([C:21]2[C:29]3[O:28][C:27]([F:31])([F:30])[O:26][C:25]=3[CH:24]=[CH:23][CH:22]=2)=O)[CH2:14][CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]>C1COCC1.CCO>[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][C:15]2([N:18]=[C:19]([C:21]3[C:29]4[O:28][C:27]([F:31])([F:30])[O:26][C:25]=4[CH:24]=[CH:23][CH:22]=3)[NH:33][C:32]2=[O:1])[CH2:14][CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]

Participants

6

Reactant 3

HCID 784Hydrogen Peroxide2×HCID 14798Sodium Hydroxide2×HCID 66817862HCID 66817862, compound

Product 1

HCID 66817774HCID 66817774, compoundYield 91.3%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A 1 N aqueous NaOH solution (0.274 ml, 0.274 mmol) and a 35% aqueous H2O2 solution (0.051 ml, 0.52 mmol) were added to a solution of 4-cyano-4-[(2,2-difluoro-benzo[1,3]dioxole-4-carbonyl)-amino]-piperidine-1-carboxylic acid tert-butyl ester (56.0 mg, 0.137 mmol) in THF (0.23 ml) at room temperature. The reaction mixture was stirred at room temperature for 43 hours, and a 35% aqueous H2O2 solution (0.030 ml, 0.31 mmol) was then further added at room temperature. After stirring at room temperature for 48 hours, the mixture was quenched with a 1 N aqueous HCl solution (0.2 ml) and concentrated under reduced pressure. A 6 N aqueous NaOH solution (0.33 ml, 2.0 mmol) was added to a suspension of the resulting residue in EtOH (1.2 ml) at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was quenched with a saturated aqueous NH4Cl solution (0.4 ml) and then concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate and washed with water, and then dried over MgSO4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/2) to give 2-(2,2-difluoro-benzo[1,3]dioxol-4-yl)-4-oxo-1,3,8-triaza-spiro[4.5]dec-1-ene-8-carboxylic acid tert-butyl ester (51.2 mg, 91%).

Workup

  1. stirringAfter stirring at room temperature for 48 hours
  2. customthe mixture was quenched with a 1 N aqueous HCl solution (0.2 ml)
  3. concentrationconcentrated under reduced pressure
  4. stirringthe mixture was stirred at room temperature for 24 hours
  5. customThe reaction mixture was quenched with a saturated aqueous NH4Cl solution (0.4 ml)
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe resulting residue was dissolved in ethyl acetate
  8. washwashed with water
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/2)

Sources & evidence

ORD record
ord-eeb76f5c1f674e0d8f103109a9724d32
Source dataset
uspto-grants-2015_10
Patent number
US09169254B2

Reaction notes

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