Pyridine → HCID 73455955, compound

HRID 1636026Notes

Reaction equation

HRID 1636026 reaction equation
[F:1][C:2]([F:25])([F:24])[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][CH3:23])=[CH:7][CH:6]=1)=O.[Cl-].[OH:27][NH3+:28].N1C=CC=CC=1>C(O)C>[F:1][C:2]([F:25])([F:24])[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][CH3:23])=[CH:7][CH:6]=1)=[N:28][OH:27]

Participants

5

Reactant 3

HCID 1049PyridineHCID 21645Hydroxylamine HClHCID 18674535HCID 18674535, compound

Product 1

HCID 73455955HCID 73455955, compoundYield 62.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

15 g (41.8 mmol) of 2,2,2-trifluoro-1-(4-dodecyloxyphenyl)-ethanone are dissolved in 100 ml of ethanol. To the solution are added 3.5 g (50.2 mmol) of hydroxylammonium chloride and 10.1 ml (125.4 mmol) of pyridine. The reaction mixture is refluxed for two hours, and the solvent is distilled off by a rotary evaporator. The residue is poured into 100 ml of water, and extracted with 100 ml and then with 50 ml of ethyl acetate. The organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine, dried over MgSO4, and concentrated. The residue is dissolved in 100 ml of methylene chloride. To the solution is added 4.2 g of conc. HCl. The reaction mixture is stirred at room temperature overnight, and poured into water. After the aqueous phase is removed, the organic phase is washed with water and brine, dried over MgSO4, and concentrated. The residue is purified by recrystallization from hexane, yielding 9.7 g of 2,2,2-trifluoro-1-(4-dodecyloxyphenyl)-ethanone oxime as a white solid with a melting point of 75-76° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ [ppm]: 0.89(t, 3H), 1.21-1.40 (m, 16H), 1.40-1.52 (m, 2H), 1.80 (m, 2H), 3.99 (t, 2H), 6.97 (d, 2H), 7.53 (d, 2H), 8.43 (s, 1H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z-conformation. When sulfuric acid is used in place of HCl, 2,2,2-trifluoro-1-(4-dodecyloxyphenyl)-ethanone oxime of the single isomer is also obtained.

Workup

  1. temperatureThe reaction mixture is refluxed for two hours
  2. distillationthe solvent is distilled off by a rotary evaporator
  3. additionThe residue is poured into 100 ml of water
  4. extractionextracted with 100 ml
  5. washThe organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. dissolutionThe residue is dissolved in 100 ml of methylene chloride
  9. additionTo the solution is added 4.2 g of conc. HCl
  10. additionpoured into water
  11. customAfter the aqueous phase is removed
  12. washthe organic phase is washed with water and brine
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated
  15. customThe residue is purified by recrystallization from hexane

Sources & evidence

ORD record
ord-e893c11b866441ac940fef470eba20eb
Source dataset
uspto-grants-2003_01
Patent number
US06512020B1

Reaction notes

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