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

HRID 1500663Notes

Reaction equation

HRID 1500663 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) 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., under an inert atmosphere. 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, and washed with water and 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 materiala saturated solution of potassium carbonate, dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-b3b5c483ac15413d917bf844324bcf59
Source dataset
uspto-grants-2015_12
Patent number
US09206174B2

Reaction notes

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