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

HRID 1782611Notes

Reaction equation

HRID 1782611 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-e2af558ef4584c13a57cdcb39236ea8c
Source dataset
uspto-grants-2009_03
Patent number
US07498468B2

Reaction notes

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