Triphenylphosphine → 1-(1-Ethynylhexyloxy)-2,3-difluorobenzene

HRID 2244835Notes

Reaction equation

HRID 2244835 reaction equation
[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[OH:9].[CH:10]#[C:11][CH:12](O)[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CC(OC)(C)C>[C:11]([CH:12]([O:9][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([F:8])[C:2]=1[F:1])[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])#[CH:10]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 131661-Octyn-3-olHCID 808792,3-DifluorophenolHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 592152391-(1-Ethynylhexyloxy)-2,3-difluorobenzene

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Procedure

42.4 g (0.33 mol) of 2,3-difluorophenol are initially introduced in 1.2 l of THF together with 50.0 ml (0.34 mol) of 1-octyn-3-ol and 94.1 g (0.36 mol) of triphenylphosphine, and a solution of 76.1 ml (0.39 mol) of DIAD in 100 ml of THF is added dropwise. After 19 h at 20° C., the mixture is diluted with MTBE, and the batch is washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO2, 1-chlorobutane), giving 1-(1-ethynylhexyloxy)-2,3-difluorobenzene as a colourless oil.

Workup

  1. washthe batch is washed with water
  2. extractionThe aqueous phase is extracted with MTBE
  3. washthe combined organic phases are washed with sat. sodium chloride soln
  4. customThe solution is dried
  5. concentrationconcentrated to dryness
  6. customThe residue is purified by column chromatography (SiO2, 1-chlorobutane)

Sources & evidence

ORD record
ord-7ca0ce9827224c2c9edb20222dc523d3
Source dataset
uspto-grants-2010_03
Patent number
US07678929B2

Reaction notes

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