tert-Butyl hydroperoxide → HCID 86716196, compound

HRID 512169Notes

Reaction equation

HRID 512169 reaction equation
[CH:1]1([CH2:4][C:5]([CH3:14])([C:8]2[CH:9]=[N:10][CH:11]=[N:12][CH:13]=2)[C:6]#[N:7])[CH2:3][CH2:2]1.C(O)([C:17](F)([F:19])[F:18])=O.C(OO)(C)(C)C.C([O-])(O)=O.[Na+]>C(Cl)Cl.O>[CH:1]1([CH2:4][C:5]([C:8]2[CH:9]=[N:10][C:11]([CH:17]([F:19])[F:18])=[N:12][CH:13]=2)([CH3:14])[C:6]#[N:7])[CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 6410tert-Butyl hydroperoxide2×HCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86716195HCID 86716195, compound

Product 1

HCID 86716196HCID 86716196, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-cyclopropyl-2-methyl-2-(pyrimidin-5-yl)propanenitrile (2.5 g, 13.4 mmol) and DMFS (7.8 g, 26.7 mmol) in DCM (40 ml) and H2O (12 ml) at room temperature was added TFA (1.5 g, 13.4 mmol) followed by slow addition of t-BuOOH (8.6 g, 67 mmol) with vigorous stirring. The reaction mixture was stirred at room temperature overnight. To the reaction mixture was added additional DMFS (7.8 g, 26.7 mmol) and t-BuOOH (8.6 g, 67 mmol). The reaction mixture was stirred at room temperature overnight. The reaction mixture was added aq. NaHCO3 and extracted with EtOAc (3×50 ml). The organic layer was dried over Na2SO4 and concentrated. The crude product was purification by column chromatography on silica gel (petroleum ether: EtOAc=4:1) to give 3-cyclopropyl-2-(2-(difluoromethyl)pyrimidin-5-yl)-2-methylpropanenitrile (1.1 g, yield: 35%). 1H NMR (CDCl3 400 MHz): δ8.97 (s, 2H), 6.82-6.55 (m, 1H), 1.92-1.90 (m, 2H), 1.85 (s, 3H), 0.71-0.65 (m, 1H), 0.60-0.57 (m, 1H), 0.51-0.47 (m, 1H), 0.26-0.20 (m, 1H), 0.03-0.00 (m, 1H).

Workup

  1. stirringThe reaction mixture was stirred at room temperature overnight
  2. extractionextracted with EtOAc (3×50 ml)
  3. dry with materialThe organic layer was dried over Na2SO4
  4. concentrationconcentrated
  5. custompurification by column chromatography on silica gel (petroleum ether: EtOAc=4:1)

Sources & evidence

ORD record
ord-e5497ead715d47bcb252860f88340a38
Source dataset
uspto-grants-2015_08
Patent number
US09102591B2

Reaction notes

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