Water → 1-(2-fluoro-4-nitrophenyl)-2,3-dihydro-1H-pyridin-4-one

HRID 896173

Reaction equation

HRID 896173 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[N:11]1[CH2:16][CH:15]=[C:14]([O:17][Si](C)(C)C)[CH2:13][CH2:12]1.C(=O)(OC)OCC=C.O>CS(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[N:11]1[CH:12]=[CH:13][C:14](=[O:17])[CH2:15][CH2:16]1

Participants

6

Reactant 3

HCID 962WaterHCID 534788Methyl 2-propen-1-yl carbonateHCID 218781391-(2-Fluoro-4-nitrophenyl)-4-[(trimethylsilyl)oxy]-1,2,3,6-tetrahydropyridine

Product 1

HCID 218776411-(2-fluoro-4-nitrophenyl)-2,3-dihydro-1H-pyridin-4-oneYield 70.5%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

To a stirring solution of 1-(2-fluoro-4-nitrophenyl)-4-[(trimethylsilyl)oxy]-1,2,3,6-tetrahydropyridine (Step 2, 100.0 g, 322 mmol) and allyl methyl carbonate (43.6 g, 386 mmol) in DMSO (625 ml) at ambient temperature is added Pd(OAc)2 (7.20 g, 32 mmol). The resulting solution is stirred under N2 at ambient temperature overnight. H2O (1 liter) is added and solvent allowed to cool to ambient temperature. The aqueous layer is extracted with EtOAc (2×800 ml), and the combined organic layers are washed with saline (800 ml) and dried over MgSO4. The solvent is removed and the residue recrystallized from EtOAc/MTBE to afford 53.6 g (70%) of the title compound as a yellow solid, 1H NMR (CDCl3) δ 2.71 (m, 2 H), 4.06 (m, 2 H), 5.41 (d, 1 H), 7.25 (m, 1 H), 7.35 (d, 1 H), 8.08 (m, 2H).

Workup

  1. temperatureto cool to ambient temperature
  2. extractionThe aqueous layer is extracted with EtOAc (2×800 ml)
  3. washthe combined organic layers are washed with saline (800 ml)
  4. dry with materialdried over MgSO4
  5. customThe solvent is removed
  6. customthe residue recrystallized from EtOAc/MTBE

Sources & evidence

ORD record
ord-69c7c77fcc554d658f1ed4bcdf52ca56
Source dataset
uspto-grants-2005_07
Patent number
US06919329B2

Linked notes

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