Pyridine → HCID 73455957, compound

HRID 1384782Notes

Reaction equation

HRID 1384782 reaction equation
[F:1][C:2]([F:29])([F:28])[C:3]([C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[CH:7][CH:6]=1)=O.[Cl-].[OH:31][NH3+:32].N1C=CC=CC=1>C(O)C>[F:1][C:2]([F:29])([F:28])[C:3]([C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[CH:7][CH:6]=1)=[N:32][OH:31]

Participants

5

Reactant 3

HCID 1049PyridineHCID 21645Hydroxylamine HClHCID 18674520HCID 18674520, compound

Product 1

HCID 73455957HCID 73455957, compoundYield 48.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

27 g (65.1 mmol) of 2,2,2-trifluoro-1-(4-hexadecyloxyphenyl)-ethanone are dissolved in 100 ml of ethanol. To the solution are added 4.5 g (65.1 mmol) of hydroxylammonium chloride and 12.9 g (163 mmol) of pyridine. The reaction mixture is refluxed for 4 hours, and the solvent is distilled off by a rotary evaporator. The residue is poured into water, and extracted with ethyl acetate. The organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine, dried over MgSO4, and concentrated. The residue is purified by recrystallization from hexane/toluene, yielding 13.5 g of 2,2,2-trifluoro-1-(4-hexadecyloxyphenyl)-ethanone oxime as a beige solid with a melting point of 76-80° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ[ppm]: 0.88 (t, 3H), 1.20-1.40 (m, 24H), 1.40-1.50 (m, 2H), 1.75-1.84 (m, 2H), 3.96-4.02 (m, 2H), 6.89(E)/6.95(Z) (d, 2H), 7.43(E)/7.52(Z) (d, 2H), 8.28(Z)/8.43(E) (br s, 1H). The signals are tentatively assigned to the E- and Z-conformations. The spectrum indicates that the compound is a mixture of E- and Z-isomers. The ratio of the mixture is estimated to be E:Z=7:3.

Workup

  1. temperatureThe reaction mixture is refluxed for 4 hours
  2. distillationthe solvent is distilled off by a rotary evaporator
  3. additionThe residue is poured into water
  4. extractionextracted with ethyl acetate
  5. washThe organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe residue is purified by recrystallization from hexane/toluene

Sources & evidence

ORD record
ord-61291d0f340a4d2cab1581484ad495e5
Source dataset
uspto-grants-2001_07
Patent number
US06261738B1

Reaction notes

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