Hydroxyamine hydrochloride → 1-(2-Fluorophenyl)-2-(1,1,1-trifluorobut-3-en-2-yloxy)ethanone oxime

HRID 1429648Notes

Reaction equation

HRID 1429648 reaction equation
Cl.[NH2:2][OH:3].C([O-])(=O)C.[Na+].[F:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:16](=O)[CH2:17][O:18][CH:19]([CH:24]=[CH2:25])[C:20]([F:23])([F:22])[F:21]>CO>[F:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:16](=[N:2][OH:3])[CH2:17][O:18][CH:19]([CH:24]=[CH2:25])[C:20]([F:23])([F:22])[F:21]

Participants

5

Reactant 3

HCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 668689851-(2-Fluorophenyl)-2-(1,1,1-trifluorobut-3-en-2-yloxy)ethanone

Product 1

HCID 866683671-(2-Fluorophenyl)-2-(1,1,1-trifluorobut-3-en-2-yloxy)ethanone oximeYield 97.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
45 °C

Procedure

To a reactor was added hydroxylamine hydrochloride (0.34 kg, 4.95 mol), sodium acetate (0.47 kg, 5.70 mol) and MeOH (2.68 L). To this suspension was charged a solution of 1-(2-fluorophenyl)-2-(1,1,1-trifluorobut-3-en-2-yloxy)ethanone (0.998 kg, 3.806 mol) in MeOH (1.8 L) and the reaction mixture was heated to 40−50° C. Upon completion (ca. 2 h) the reaction mixture was cooled to rt, and filtered over Celite (0.5 wt) and rinsed with EtOAc (3.0 L). The filtrate was concentrated under vacuum and to the resulting residue was added methyl tert-butyl ether (6.3 L), water (0.94 L) and sat. aq. NaHCO3 (2.5 L). The organic phase was washed once with water (1.6 L) and sat. aq. NaCl (0.1 L). The organic phase was concentrated under vacuum to afford the title compound as an oil (1.03 kg, 95.0%). 1H NMR (500 MHz, CDCl3) δ ppm 7.49-7.35 (m, 2H), 7.24-7.06 (m, 2H), 5.78-5.65 (m, 1H), 5.54-5.40 (m, 2H), 4.89-4.81 (m, 1H), 4.53 (d, J=12.6 Hz, 1H), 4.47 (d, J=12.6 Hz, 0.5H), 4.27-4.18 (m, 1H), 4.13-4.05 (m, 0.5H).

Workup

  1. temperatureUpon completion (ca. 2 h) the reaction mixture was cooled to rt
  2. filtrationfiltered over Celite (0.5 wt)
  3. washrinsed with EtOAc (3.0 L)
  4. concentrationThe filtrate was concentrated under vacuum and to the resulting residue
  5. additionwas added methyl tert-butyl ether (6.3 L), water (0.94 L) and sat. aq. NaHCO3 (2.5 L)
  6. washThe organic phase was washed once with water (1.6 L) and sat. aq. NaCl (0.1 L)
  7. concentrationThe organic phase was concentrated under vacuum

Sources & evidence

ORD record
ord-ad376f6e983e4e3ba8c115cf880029aa
Source dataset
uspto-grants-2015_01
Patent number
US08940734B2

Reaction notes

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