Tributylvinyltin → 5-Ethenyl-2-(trifluoromethyl)pyridine

HRID 710738Notes

Reaction equation

HRID 710738 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]([F:11])([F:10])[F:9])=[N:6][CH:7]=1.[CH:12]([Sn](CCCC)(CCCC)CCCC)=[CH2:13]>CN(C=O)C.C1COCC1.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>[F:9][C:8]([F:11])([F:10])[C:5]1[CH:4]=[CH:3][C:2]([CH:12]=[CH2:13])=[CH:7][N:6]=1

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 27611975-Bromo-2-(trifluoromethyl)pyridine

Product 1

HCID 574168485-Ethenyl-2-(trifluoromethyl)pyridineYield 1,324.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 21974620tetrahydrofuran N,N-dimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

2 g of 5-bromo-2-(trifluoromethyl)pyridine was dissolved in DMF:THF (3:1, 12 mL). vinyltributyltin (3 g) and tetrakis(triphenylphosphine)palladium (135 mg) were added to this solution. The reaction mixture was degassed and purged with nitrogen for 5 min and then heated at 100° C. for 2 h. at which point the reaction was found complete (monitored by TLC). The reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure (Caution: product may be volatile) and the residue was purified by SiO2 chromatography (100-200 mesh, eluent:hexane-ethyl acetate gradient). The requisite fractions were concentrated below 40° C. under reduced pressure to obtain 20.3 g of 2-(trifluoromethyl)-5-vinylpyridine as oil.

Workup

  1. customThe reaction mixture was degassed
  2. custompurged with nitrogen for 5 min
  3. additionThe reaction mixture was diluted with water
  4. extractionextracted with ethyl acetate
  5. dry with materialThe combined organic layer was dried over anhydrous sodium sulfate
  6. customevaporated under reduced pressure (Caution: product may be volatile)
  7. customthe residue was purified by SiO2 chromatography (100-200 mesh, eluent:hexane-ethyl acetate gradient)
  8. concentrationThe requisite fractions were concentrated below 40° C. under reduced pressure

Sources & evidence

ORD record
ord-d96a637b54c742c78d87ed6c93443e88
Source dataset
uspto-grants-2015_11
Patent number
US09181240B2

Reaction notes

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