Chlorotrimethylsilane → (4-Chloro-2,6-difluorophenyl)trimethylsilane

HRID 2249384Notes

Reaction equation

HRID 2249384 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([Cl:9])[CH:5]=[C:6]([F:8])[CH:7]=1.CN(C)CCN(C)C.C([Li])CCC.[CH3:23][Si:24](Cl)([CH3:26])[CH3:25].[Cl-].[NH4+]>C1COCC1>[Cl:9][C:4]1[CH:3]=[C:2]([F:1])[C:7]([Si:24]([CH3:26])([CH3:25])[CH3:23])=[C:6]([F:8])[CH:5]=1

Participants

7

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 25517Ammonium ChlorideHCID 137000Benzene, 1-chloro-3,5-difluoro-HCID 178418339Butyllithium

Product 1

HCID 18935733(4-Chloro-2,6-difluorophenyl)trimethylsilaneYield 89.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 3,5-difluoro-1-chlorobenzene (10.0 g, 67 mmol) and tetramethylethlenediamine (TMEDA; 7.8 g, 67 mmol) in THF (75 mL) at −75° C., was added n-butyl lithium (2.5M, 68 mmol) and the resulting solution stirred for 30 minutes. A solution of trimethylsilyl chloride (7.6 g, 70 mmol) in THF (15 mL) was added and the solution allowed to warm to ambient temperature and stir for 25 hours. Ammonium chloride (saturated solution 15 mL) was added and the mixture extracted with ethyl ether (2×100 mL) and the combined extracts washed with brine, dried (sodium sulfate) and concentrated. The residual oil was distilled to give 1-chloro-3,5-difluoro-4-trimethylsilylbenzene (13.0 g, 60 mmol): bp 70-75° C.

Workup

  1. stirringstir for 25 hours
  2. extractionthe mixture extracted with ethyl ether (2×100 mL)
  3. washthe combined extracts washed with brine
  4. dry with materialdried (sodium sulfate)
  5. concentrationconcentrated
  6. distillationThe residual oil was distilled

Sources & evidence

ORD record
ord-81c0de7e90984bc08a565a80c509d0f0
Source dataset
uspto-grants-2008_01
Patent number
US07314849B2

Reaction notes

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