Triethylamine → 2-Chloro-4-ethenylpyrimidine

HRID 410639Notes

Reaction equation

HRID 410639 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[CH:5]=[CH:4][N:3]=1.[CH:9]([B-](F)(F)F)=[CH2:10].[K+].C(N(CC)CC)C>C(O)CC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[Cl:1][C:2]1[N:7]=[C:6]([CH:9]=[CH2:10])[CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 775312,4-DichloropyrimidineHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 450801732-Chloro-4-ethenylpyrimidine

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 10311-PropanolSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of 2,4-dichloropyrimidine (4.4 g, 29.5 mmol), potassium vinyltrifluoroborate (4.58 g, 32.5 mmol), PdCl2(dppf)-CH2Cl2 (1.21 g, 1.48 mmol) and triethylamine (4.12 mL, 29.5 mmol) in nPrOH (148 mL) was purged with nitrogen for 15 min, heated to 100° C. for 5 h, and then cooled to room temperature. The mixture was treated with water and extracted with EtOAc (×3). The combined organics were washed with brine, dried (sodium sulfate), filtered and concentrated, and purified by flash chromotography to afford 2-chloro-4-ethenylpyrimidine as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 8.56 (d, J=5.1, 1H), 7.21 (d, J=5.1, 1H), 6.70 (dd, J=10.6, 17.4, 1H), 6.57-6.51 (m, 1H), 5.79 (dd, J=0.8, 10.6, 1H).

Workup

  1. customwas purged with nitrogen for 15 min
  2. temperaturecooled to room temperature
  3. additionThe mixture was treated with water
  4. extractionextracted with EtOAc (×3)
  5. washThe combined organics were washed with brine
  6. dry with materialdried (sodium sulfate)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by flash chromotography

Sources & evidence

ORD record
ord-d00954c6fb7749519cffcb019ec4d981
Source dataset
uspto-grants-2014_06
Patent number
US08759366B2

Reaction notes

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