4-Bromotoluene → 2,3,4,6-Tetrafluoro-N-(4-methylphenyl)benzenamine

HRID 603335Notes

Reaction equation

HRID 603335 reaction equation
[F:1][C:2]1[C:8]([F:9])=[C:7]([F:10])[CH:6]=[C:5]([F:11])[C:3]=1[NH2:4].Br[C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1.CC(C)([O-])C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=CC=1>[F:1][C:2]1[C:8]([F:9])=[C:7]([F:10])[CH:6]=[C:5]([F:11])[C:3]=1[NH:4][C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 78054-BromotolueneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 1230482,3,4,6-TetrafluoroanilineHCID 23676156Sodium t-butoxide

Product 1

HCID 579521482,3,4,6-Tetrafluoro-N-(4-methylphenyl)benzenamineYield 81.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 2,3,4,6-tetrafluoroaniline (0.72 g, 4.4 mmol), 4-bromotoluene (0.8 g, 4.7 mmol), toluene (55 ml), sodium tert-butoxide (0.8 g, 8.3 mmol), tri-tert-butylphosphine (130 mg, 0.64 mmol) and bis-dibenzylideneacetone-palladium(0) (125 mg, 0.2 mmol) is heated under nitrogen to 85° C. for 3 h. After cooling, water (50 ml), concentrated aqu. HCl (10 ml) and hyflo (1 g) is added and stirring is continued for about one hour followed by filtration. The organic phase is washed with water twice, evaporated and the residue is subjected to flash chromatography on silica (45 g) using heptane/toluene (2:1) as the eluent to afford N-(2′,3′,4′,6′-Tetrafluorophenyl)-4-methylaniline (0.92 g, 3.6 mmol) as an oil which crystallises (mp. 64-65° C.).

Workup

  1. temperatureAfter cooling
  2. concentrationwater (50 ml), concentrated aqu
  3. additionHCl (10 ml) and hyflo (1 g) is added
  4. filtrationfollowed by filtration
  5. washThe organic phase is washed with water twice
  6. customevaporated

Sources & evidence

ORD record
ord-1d660ab28935430097d4b2316225c737
Source dataset
uspto-grants-2011_03
Patent number
US07906677B2

Reaction notes

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