N,N-Dimethylaniline → HCID 59160675, compound

HRID 1500050Notes

Reaction equation

HRID 1500050 reaction equation
[CH2:1]([O:4][C:5]1[N:10]=[C:9](O)[C:8]([F:12])=[CH:7][N:6]=1)[CH:2]=[CH2:3].CN(C)C1C=CC=CC=1.P(Cl)(Cl)([Cl:24])=O.C(#N)C>CCOCC>[CH2:1]([O:4][C:5]1[N:10]=[C:9]([Cl:24])[C:8]([F:12])=[CH:7][N:6]=1)[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 949N,N-DimethylanilineHCID 6342AcetonitrileHCID 24813Phosphorus oxychlorideHCID 178458938HCID 178458938, compound

Product 1

HCID 59160675HCID 59160675, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

A 250 mL round bottom flask was charged with 2-(allyloxy)-5-fluoropyrimidin-4-ol 4.96 g, 29.2 mmol), N,N-dimethylaniline (5.45 mL, 43.0 mmol), phosphorous oxychloride (3.30 mL, 35.4 mmol), and acetonitrile (60 mL). The resulting solution was heated at 80° C. for 1 h. After cooling to room temperature, the crude material was diluted with Et2O (300 mL) and was washed with 1.0 M aqueous NaH2PO4 (150 mL×2) and saturated aqueous NaCl (150 mL). The organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure to obtain 2-(allyloxy)-4-chloro-5-fluoropyrimidine contaminated with N,N-dimethylaniline (6.71 g, 72.5% pure, 89% calcd.) as a brown oil: 1H NMR (300 MHz, DMSO-d6) δ 8.78 (bs, 1H), 6.04 (m, 1H), 5.38 (d, J=16.8 Hz, 1H), 5.26 (d, J=10.3 Hz, 1H), 4.82 (dd, J=0.8, 5.3 Hz, 2H); MS (EI) m/z 187 (M+H)+.

Workup

  1. temperatureAfter cooling to room temperature
  2. washwas washed with 1.0 M aqueous NaH2PO4 (150 mL×2) and saturated aqueous NaCl (150 mL)
  3. dry with materialThe organic layers were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a0e2cba697e64bfaa90257d854eba9e3
Source dataset
uspto-grants-2015_12
Patent number
US09204653B2

Reaction notes

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