Toluene → HCID 13730360, compound

HRID 2038373Notes

Reaction equation

HRID 2038373 reaction equation
C1(C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C(=CC=CC=2)C=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1.Br[C:48]1[CH:49]=[C:50]([C:55]#[N:56])[CH:51]=[C:52]([F:54])[CH:53]=1.C1(C)C=CC=CC=1.[CH2:64]([O:66]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:65]>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]>[C:64]([C:48]1[CH:49]=[C:50]([C:55]#[N:56])[CH:51]=[C:52]([F:54])[CH:53]=1)(=[O:66])[CH3:65]

Participants

6

Reactant 4

HCID 1140TolueneHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 634876Binap, (A+-)-HCID 27833303-Bromo-5-fluorobenzonitrile

Product 1

HCID 13730360HCID 13730360, compound

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

Under an argon atmosphere, 824 mg (0.900 mmol) of tris(dibenzylideneacetone)dipalladium and 1.23 g (1.98 mmol) of rac-1,1′-binaphthalene-2,2′-diylbis(diphenylphosphane) are added to 9.00 g (45.0 mmol) of 3-bromo-5-fluorobenzenecarbonitrile in toluene (300 mol). After the addition of 19.5 g (54.0 mmol) of (1-ethoxyvinyl)tributylstannane, the mixture is stirred under reflux overnight. The reaction mixture is subsequently concentrated and the residue is taken up in 300 ml of THF. After the addition of 100 ml of an aqueous 2N hydrogen chloride solution, the mixture is stirred at room temperature for 2 h. The reaction mixture is subsequently neutralized using a saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. The combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. The crude product is purified by flash chromatography (mobile phase: cyclohexane/ethyl acetate 9:1). 7.11 g (97% of theory) of the title compound are obtained.

Workup

  1. temperatureunder reflux overnight
  2. concentrationThe reaction mixture is subsequently concentrated
  3. additionAfter the addition of 100 ml of an aqueous 2N hydrogen chloride solution
  4. stirringthe mixture is stirred at room temperature for 2 h
  5. extractionextracted with ethyl acetate
  6. dry with materialThe combined organic phases are dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe crude product is purified by flash chromatography (mobile phase: cyclohexane/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-d4d499a166534c8bb9dd19a288bb1d9d
Source dataset
uspto-grants-2013_11
Patent number
US08575357B2

Reaction notes

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