Hexane → Ethyl 2-fluoro-3-vinylbenzoate

HRID 2233780Notes

Reaction equation

HRID 2233780 reaction equation
Br[C:2]1[C:3]([F:13])=[C:4]([CH:10]=[CH:11][CH:12]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6].[C:14](P(C(C)(C)C)C(C)(C)C)(C)(C)[CH3:15].CCCCCC.[F-].[K+]>C([Sn](CCCC)(CCCC)C=C)CCC.C(OCC)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[F:13][C:3]1[C:2]([CH:14]=[CH2:15])=[CH:12][CH:11]=[CH:10][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

9

Reactant 4

HCID 8058HexaneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 17832538Ethyl 3-bromo-2-fluorobenzoate

Product 1

HCID 68451554Ethyl 2-fluoro-3-vinylbenzoateYield 97%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 81998TributylvinyltinSolvent

Procedure

A 12.76 g portion of ethyl 3-bromo-2-fluorobenzoate was dissolved in 50 ml of Tol solution, 15.8 ml of tributyl(vinyl)tin, 236 mg of tris(dibenzylideneacetone)dipalladium and 1.25 ml of tri-tert-butylphosphine 10 wt % hexane solution were added thereto in order, and stirred at room temperature for 13 hours in an atmosphere of argon. This was diluted with 300 ml of diethyl ether, mixed with 25 g of potassium fluoride and 5 ml of purified water and stirred for 30 minutes, the insoluble matter was filtered using a Kiriyama funnel, and then the mother liquid was concentrated. The residue was purified by a silica gel column chromatography (hexane:ethyl acetate=40:1) to obtain 10.3 g (97%) of ethyl 2-fluoro-3-vinylbenzoate (Reference Example 17-1).

Workup

  1. additionwere added
  2. stirringstirred for 30 minutes
  3. filtrationthe insoluble matter was filtered
  4. concentrationthe mother liquid was concentrated
  5. customThe residue was purified by a silica gel column chromatography (hexane:ethyl acetate=40:1)

Sources & evidence

ORD record
ord-251f5ceb689f4d03bf0aac5e723587d9
Source dataset
uspto-grants-2010_05
Patent number
US07709519B2

Reaction notes

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