Ethanone, 1-(4-chloro-3-fluorophenyl)-2-[[(1,1-dimethylethyl)dimethylsilyl]oxy]- → Tert-butyl (2-(4-chloro-3-fluorophenyl)allyloxy)dimethylsilane

HRID 1774237Notes

Reaction equation

HRID 1774237 reaction equation
[Li][CH2:2]CCC.[Si:6]([O:13][CH2:14][C:15]([C:17]1[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([F:24])[CH:18]=1)=O)([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:9]([Si:6]([O:13][CH2:14][C:15]([C:17]1[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([F:24])[CH:18]=1)=[CH2:2])([CH3:8])[CH3:7])([CH3:12])([CH3:11])[CH3:10]

Participants

5

Reactant 2

HCID 68294408Ethanone, 1-(4-chloro-3-fluorophenyl)-2-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-HCID 178418339Butyllithium

Product 1

HCID 86696739Tert-butyl (2-(4-chloro-3-fluorophenyl)allyloxy)dimethylsilaneYield 40%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

n-BuLi (2.5N, 8.0 mL) was added at −78° C. to a mixture of methyltriphenylphosphonium bromide (5.6 g, 0.15 mol) in THF (50 mL). After being stirred for 0.5 hours, 2-(tert-butyldimethylsilyloxy)-1-(4-chloro-3-fluorophenyl)ethanone (3.9 g, 0.013 mol) was added to the reaction mixture. The mixture was then stirred for 2 hours at 25° C. After quenching with saturated NH4Cl (100 mL), the reaction mixture was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried and concentrated. The residue was purified by silica gel column chromatography eluting with petroleum ether to give tert-butyl (2-(4-chloro-3-fluorophenyl)allyloxy)dimethylsilane (1.6 g, 40% yield).

Workup

  1. stirringThe mixture was then stirred for 2 hours at 25° C
  2. customAfter quenching with saturated NH4Cl (100 mL)
  3. extractionthe reaction mixture was extracted with ethyl acetate (3×50 mL)
  4. customThe combined organic layers were dried
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography
  7. washeluting with petroleum ether

Sources & evidence

ORD record
ord-17ff1fc21e534399810462c3ae6c9d6b
Source dataset
uspto-grants-2016_02
Patent number
US09259470B2

Reaction notes

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