Hydrogen Bromide → 3'-(Trifluoromethyl)acetophenone

HRID 634976Notes

Reaction equation

HRID 634976 reaction equation
Br.[F:2][C:3]([F:12])([F:11])[C:4]1[CH:5]=[C:6]([CH:8]=[CH:9][CH:10]=1)N.N([O-])=[O:14].[Na+].[CH:17](=NO)[CH3:18]>O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[CH3:18][C:17]([C:6]1[CH:8]=[CH:9][CH:10]=[C:4]([C:3]([F:12])([F:11])[F:2])[CH:5]=1)=[O:14]

Participants

7

Reactant 4

HCID 260Hydrogen BromideHCID 73753-(Trifluoromethyl)anilineHCID 7863AldoximeHCID 23668193Sodium Nitrite

Product 1

HCID 676823'-(Trifluoromethyl)acetophenoneYield 48%

Reagents, catalysts & solvents 2

HCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolvent3×

Conditions

Temperature
-6 °C

Procedure

Under nitrogen, 297 g of water and 246 g of hydrobromic acid (48% strength) were initially charged, and 80 g of 3-trifluoromethylaniline were introduced. The suspension that formed was stirred and cooled to −6° C. Over a period of 30 minutes, 37 g of sodium nitrite dissolved in 78 g of water were now added dropwise, and the mixture was stirred for another 30 minutes. The solution that had formed was subsequently, at 30° C., metered into an initial charge of 6 g of copper sulphate pentahydrate dissolved in 26 g of water. This mixture was now added dropwise over a period of 1.5 hours to an initial charge of 45 g of acetaldoxime, the temperature being controlled in such a manner that it did not exceed 40° C. The mixture was subsequently heated to 100° C. The crude product was distilled off together with water. After the water had been removed from the distillate, the crude product was distilled over a column. 44 g (=48% of theory) of 3-trifluoromethylacetophenone were obtained.

Workup

  1. customThe suspension that formed
  2. additionwere now added dropwise
  3. stirringthe mixture was stirred for another 30 minutes
  4. customThe solution that had formed
  5. customwas subsequently, at 30° C.
  6. additionThis mixture was now added dropwise over a period of 1.5 hours to
  7. customdid not exceed 40° C
  8. temperatureThe mixture was subsequently heated to 100° C
  9. distillationThe crude product was distilled off together with water
  10. customAfter the water had been removed from the distillate
  11. distillationthe crude product was distilled over a column

Sources & evidence

ORD record
ord-71510bc40d4b4ec4a4f129ea7d51cf66
Source dataset
uspto-grants-2001_02
Patent number
US06184417B2

Reaction notes

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