tert-Butyl hydroperoxide → HCID 86716005, compound

HRID 514891Notes

Reaction equation

HRID 514891 reaction equation
[O:1]1[CH2:6][CH2:5][N:4]([CH:7]([C:10]2[CH:11]=[N:12][CH:13]=[N:14][CH:15]=2)[C:8]#[N:9])[CH2:3][CH2:2]1.C(O)([C:18](F)([F:20])[F:19])=O.O(C(C)(C)C)O.C([O-])(O)=O.[Na+]>C(Cl)Cl.O>[F:19][CH:18]([F:20])[C:13]1[N:12]=[CH:11][C:10]([CH:7]([N:4]2[CH2:5][CH2:6][O:1][CH2:2][CH2:3]2)[C:8]#[N:9])=[CH:15][N:14]=1

Participants

7

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86716006HCID 86716006, compound

Product 1

HCID 86716005HCID 86716005, compoundYield 11.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-morpholino-2-(pyrimidin-5-yl)acetonitrile (1.03 g, 5.04 mmol) and DFMS (4 g, 13.61 mmol) in DCM (40 mL) and H2O (16 mL) at room temperature was added CF3COOH (575 mg, 5.04 mmol) followed by slow addition of 2-hydroperoxy-2-methylpropane (3.24 g, 70% solution in H2O) with vigorous stirring. The reaction mixture was stirred at room temperature overnight. The reaction mixture was portioned between DCM (50 mL) and saturated NaHCO3 solution (50 mL), the organic layer was separated and the aqueous layer was extracted with DCM (5 mL×3). The organic layer was washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by Prep-TLC (Petroleum ether:EtOAc=10:12:1) to give 2-(2-(difluoromethyl)pyrimidin-5-yl)-2-morpholinoacetonitrile (150 mg, yield: 11.7%). 1H NMR (CDCl3 400 MHz): δ9.01 (d, J=10.0 Hz, 2H), 6.67 (t, J=54.4 Hz, 1H), 4.91 (s, 1H), 3.95-3.62 (m, 4H), 2.81-2.46 (m, 4H).

Workup

  1. customthe organic layer was separated
  2. extractionthe aqueous layer was extracted with DCM (5 mL×3)
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. customThe crude product was purified by Prep-TLC (Petroleum ether:EtOAc=10:12:1)

Sources & evidence

ORD record
ord-807e19d29be74113a0244a8a2b5ef85e
Source dataset
uspto-grants-2015_08
Patent number
US09108938B2

Reaction notes

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