Tributylvinyltin → 1-(3-Chloro-5-vinyl-2-pyridyl)cyclopropanecarbonitrile

HRID 578866Notes

Reaction equation

HRID 578866 reaction equation
Br[C:2]1[CH:3]=[C:4]([Cl:13])[C:5]([C:8]2([C:11]#[N:12])[CH2:10][CH2:9]2)=[N:6][CH:7]=1.[CH:14]([Sn](CCCC)(CCCC)CCCC)=[CH2:15]>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:13][C:4]1[C:5]([C:8]2([C:11]#[N:12])[CH2:10][CH2:9]2)=[N:6][CH:7]=[C:2]([CH:14]=[CH2:15])[CH:3]=1

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 715592791-(5-Bromo-3-chloropyridin-2-yl)cyclopropane-1-carbonitrile

Product 1

HCID 895443761-(3-Chloro-5-vinyl-2-pyridyl)cyclopropanecarbonitrileYield 50.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

4.7 g of 1-(5-Bromo-3-chloro-pyridin-2-yl)-cyclopropanecarbonitrile (step 2 of PREPARATION EXAMPLE 3) was dissolved in 40 ml anhydrous toluene, then 700 mg of tetrakis(triphenylphosphine)palladium(0) and 9.0 g vinyltributylstannane were added under a nitrogen atmosphere. The reaction mixture was heated on reflux for 3 hours. After cooling to ambient temperature, the reaction mixture was filtered, the filtrate was diluted with 100 ml of ethyl acetate, then washed with water and with saturated potassium fluoride solution. The organic layer was dried over anhydrous sodium sulfate and concentrated. Crude material was obtained as a dark oil, which was purified by flash chromatography on silica gel with heptane/ethyl acetate as a solvent. Thus, 1.9 g of 1-(3-chloro-5-vinyl-2-pyridyl)cyclopropanecarbonitrile was obtained as a yellow oil. 1H-NMR (CDCl3): 8.40 ppm (s, 1H), 7.78 ppm (s, 1H), 6.67 ppm (dd, 1H), 5.87 ppm (d, 1H), 5.50 ppm (d, 1H), 1.77 ppm (m, 2H), 1.63 ppm (m, 2H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureon reflux for 3 hours
  3. filtrationthe reaction mixture was filtered
  4. additionthe filtrate was diluted with 100 ml of ethyl acetate
  5. washwashed with water and with saturated potassium fluoride solution
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. concentrationconcentrated
  8. customCrude material was obtained as a dark oil, which
  9. customwas purified by flash chromatography on silica gel with heptane/ethyl acetate as a solvent

Sources & evidence

ORD record
ord-2d544ae3519748b3bf2348f5d3041561
Source dataset
uspto-grants-2015_05
Patent number
US09040708B2

Reaction notes

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