Methyl Ethyl Ketone → 2,3-Dimethyl-4-(2,2,3,3,3-pentafluoropropoxy)pyridine-1-oxide

HRID 843979Notes

Reaction equation

HRID 843979 reaction equation
[CH3:1][C:2]1[C:7]([CH3:8])=[C:6]([N+]([O-])=O)[CH:5]=[CH:4][N+:3]=1[O-:12].C(C(C)=O)C.[F:18][C:19]([F:26])([C:22]([F:25])([F:24])[F:23])[CH2:20][OH:21].C(=O)([O-])[O-].[K+].[K+]>CN(C)P(=O)(N(C)C)N(C)C>[CH3:1][C:2]1[C:7]([CH3:8])=[C:6]([O:21][CH2:20][C:19]([F:26])([F:18])[C:22]([F:25])([F:24])[F:23])[CH:5]=[CH:4][N+:3]=1[O-:12]

Participants

6

Reactant 4

HCID 6569Methyl Ethyl KetoneHCID 98722,2,3,3,3-PentafluoropropanolHCID 11430Potassium CarbonateHCID 1482232,3-Dimethyl-4-nitropyridine-N-oxide

Product 1

HCID 136547942,3-Dimethyl-4-(2,2,3,3,3-pentafluoropropoxy)pyridine-1-oxide

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
75 °C

Procedure

A mixture of 2,3-dimethyl-4-nitropyridine-1-oxide (2.0 g), methyl ethyl ketone (30 ml), 2,2,3,3,3-pentafluoropropanol (3.05 ml), anhydrous potassium carbonate (3.29 g) and hexamethylphosphoric acid triamide (2.07 g) was heated at 70-80° C. with stirring for 4.5 days. Then, the insoluble matter was filtered off and the filtrate was concentrated. Water was added to the residue and the mixture was extracted with ethyl acetate. The extract layer was dried over magnesium sulfate, then the solvent was distilled off, and the residue was applied to a silica gel column (50 g). Elution with chloroform-methanol (10:1) and recrystallization from ethyl acetate-hexane gave 2.4 g of 2,3-dimethyl-4-(2,2,3,3,3-pentafluoropropoxy)pyridine-1-oxide as colorless needles. Melting point 148-149° C.

Workup

  1. filtrationThen, the insoluble matter was filtered off
  2. concentrationthe filtrate was concentrated
  3. additionWater was added to the residue
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe extract layer was dried over magnesium sulfate
  6. distillationthe solvent was distilled off
  7. washElution
  8. customwith chloroform-methanol (10:1) and recrystallization from ethyl acetate-hexane

Sources & evidence

ORD record
ord-03f1615a58454994848af45cfa968c4c
Source dataset
uspto-grants-2002_04
Patent number
US06380234B1

Reaction notes

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