N-bromobutanimide → N-[4-(Bromomethyl)-3-(trifluoromethyl)phenyl]-2,2,2-trifluoroacetamide

HRID 1038728Notes

Reaction equation

HRID 1038728 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:14])[C:10]([F:13])([F:12])[F:11])=[CH:4][C:3]=1[C:15]([F:18])([F:17])[F:16].[Br:19]N1C(=O)CCC1=O>C(OCCCC)(=O)C>[Br:19][CH2:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:14])[C:10]([F:13])([F:12])[F:11])=[CH:4][C:3]=1[C:15]([F:16])([F:17])[F:18]

Participants

4

Reactant 2

HCID 67184N-bromobutanimide2×HCID 573517652,2,2-Trifluoro-N-[4-methyl-3-(trifluoromethyl)phenyl]acetamide

Product 1

HCID 57351764N-[4-(Bromomethyl)-3-(trifluoromethyl)phenyl]-2,2,2-trifluoroacetamide

Reagents, catalysts & solvents 1

HCID 31272Butyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 60.9 g (224.6 mmol) of N-(4-methyl-3-trifluoromethyl-phenyl)-2,2,2-trifluoro-acetamide in 830 ml n-butyl acetate under a nitrogen atmosphere, 44 g (247 mmol) N-bromosuccinimide and 830 mg (5 mmol) azo-iso-butyronitrile are added. The suspension is heated up to 60° C. and then illuminated for 30 min by a Phillips low-voltage lamp (500 W; 10500 lm), whereby the temperature rises to 70-75° C. and a clear brown solution is formed. There is still remaining educt detectable, therefore another 22 g N-bromosuccinimide are added in 3 portions. After totally 6 h illumination, the resulting solid is filtered off and discarded and the filtrate concentrated. The residue is distributed between 2 l CH2Cl2 and 1 l H2O and the aqueous layer extracted with 1 l CH2Cl2. The organic phases are washed 4 times with 1 l H2O, 0.5 l brine, dried (Na2SO4) and concentrated. Column chromatography (SiO2; hexane/CH2Cl2 2:1→1:1) and crystallization from CH2Cl2/hexane yields the title compound: m.p.: 119-120° C.

Workup

  1. customilluminated for 30 min by a Phillips low-voltage lamp (500 W; 10500 lm), whereby the temperature
  2. customrises to 70-75° C.
  3. customa clear brown solution is formed
  4. filtrationthe resulting solid is filtered off
  5. concentrationthe filtrate concentrated
  6. extractionthe aqueous layer extracted with 1 l CH2Cl2
  7. washThe organic phases are washed 4 times with 1 l H2O, 0.5 l brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated
  10. customColumn chromatography (SiO2; hexane/CH2Cl2 2:1→1:1) and crystallization from CH2Cl2/hexane

Sources & evidence

ORD record
ord-c9430bf6161a4e93ada537c9d420dbf3
Source dataset
uspto-grants-2013_10
Patent number
US08552002B2

Reaction notes

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