Sodium chlorodifluoroacetate → 1-difluoromethyl-5-nitro-1H-pyridin-2-one

HRID 2042676Notes

Reaction equation

HRID 2042676 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.Cl[C:12]([F:17])([F:16])C([O-])=O.[Na+]>C(#N)C>[F:16][CH:12]([F:17])[O:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[F:16][CH:12]([F:17])[N:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]1=[O:1]

Participants

5

Reactant 2

HCID 2734985Sodium chlorodifluoroacetateHCID 178526703HCID 178526703, compound

Product 2

HCID 160796311-difluoromethyl-5-nitro-1H-pyridin-2-oneHCID 534037522-(Difluoromethoxy)-5-nitropyridine

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

2-Hydroxy-5-nitro-pyridine (5 g) was treated with sodium chlorodifluoro-acetate (11.5 g) in refluxing acetonitrile (186 ml) for 2 days. The solvent was evaporated, the residue poured into ethyl acetate, washed with brine, dried over sodium sulfate and then concentrated in vacuo. Chromatography on silica gel (eluent: hexane/ethyl acetate 1:1) afforded 2-difluoromethoxy-5-nitro-pyridine (1 g) and 1-difluoromethyl-5-nitro-1H-pyridin-2-one (90 mg). 2-Difluoromethoxy-5-nitro-pyridine: MS (ES+) 191 (MH+); 1H NMR (400 MHz, CDCl3) 7.05 (d, 1H), 7.51 (t, 1H), 8.53 (dd, 1H), 9.09 (d, 1H). 1-Difluoromethyl-5-nitro-1H-pyridin-2-one: MS (ES+) 191 (MH+); 1H NMR (400 MHz, CDCl3) 6.65 (d, 1H), 7.63 (t, 1H), 8.14 (dd, 1H), 8.73 (d, 1H).

Workup

  1. customThe solvent was evaporated
  2. additionthe residue poured into ethyl acetate
  3. washwashed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6669b80800614181ba543cfcbf9acaf9
Source dataset
uspto-grants-2013_11
Patent number
US08586593B2

Reaction notes

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