Chlorotrimethylsilane → 2-Fluoro-4-(trimethylsilyl)aniline

HRID 453391Notes

Reaction equation

HRID 453391 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([F:9])[CH:3]=1.[Li]CCCC.[CH3:15][Si:16](Cl)([CH3:18])[CH3:17]>C1COCC1>[F:9][C:4]1[CH:3]=[C:2]([Si:16]([CH3:18])([CH3:17])[CH3:15])[CH:7]=[CH:6][C:5]=1[NH2:8]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 1230504-Bromo-2-fluoroanilineHCID 178418339Butyllithium

Product 1

HCID 595965992-Fluoro-4-(trimethylsilyl)anilineYield 81%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-bromo-2-fluoro-phenylamine (114 g, 0.6 mol) in anhydrous THF (750 mL) under inert atmosphere at −78° C. was added a 1.6M solution of nBuLi in hexanes (1500 mL, 2.4 mol) dropwise keeping the internal temperature below −60° C. The reaction mixture was treated dropwise with TMSCl (256 mL, 2.0 mol), keeping the internal temperature below −60° C. The reaction mixture was allowed to warm to 0° C. over a 1 hour period and poured into ice-cold 2M HCl (ca 1 L). The mixture was vigorously stirred for 10 min, then the organic layer was separated, washed with water followed by a saturated solution of potassium carbonate, dried (Na2SO4), filtered and concentrated to give the title compound as a light brown oil (89 g, 81%).

Workup

  1. customthe internal temperature below −60° C
  2. customthe internal temperature below −60° C
  3. customthe organic layer was separated
  4. washwashed with water
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-240877a350684a08a6e6085c657b5721
Source dataset
uspto-grants-2013_07
Patent number
US08492427B2

Reaction notes

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