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

HRID 1873308Notes

Reaction equation

HRID 1873308 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

2.4 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 RT, the batch is diluted with MTBE and washed with water. The aqueous phase is extracted with MTBE, and the combined organic phases are washed with saturated sodium chloride solution. The solution is dried using sodium sulfate and evaporated 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. washwashed with water
  2. extractionThe aqueous phase is extracted with MTBE
  3. washthe combined organic phases are washed with saturated sodium chloride solution
  4. customThe solution is dried
  5. customevaporated to dryness
  6. customThe residue is purified by column chromatography (SiO2, 1-chlorobutane)

Sources & evidence

ORD record
ord-99a9c6d81ce54503a22202bff0fb1439
Source dataset
uspto-grants-2012_11
Patent number
US08303844B2

Reaction notes

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