Lithium Chloride → 4-Chloro-2,6-dimethyl-5-(1-ethoxyvinyl)pyrimidine

HRID 129017Notes

Reaction equation

HRID 129017 reaction equation
[Cl:1][C:2]1[C:7](I)=[C:6]([CH3:9])[N:5]=[C:4]([CH3:10])[N:3]=1.[CH2:11]([O:13][C:14]([Sn](CCCC)(CCCC)CCCC)=[CH2:15])[CH3:12].[Cl-].[Li+].[F-].[K+]>CCOC(C)=O.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.O1CCOCC1>[Cl:1][C:2]1[C:7]([C:11]([O:13][CH2:14][CH3:15])=[CH2:12])=[C:6]([CH3:9])[N:5]=[C:4]([CH3:10])[N:3]=1

Participants

8

Reactant 4

HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 14911174-Chloro-5-iodo-2,6-dimethylpyrimidine

Product 1

HCID 107272924-Chloro-2,6-dimethyl-5-(1-ethoxyvinyl)pyrimidineYield 61%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 4-chloro-2,6-dimethyl-5-iodopyrimidine (13.5 g, 0.050 mol), (1ethoxyvinyl)tributyltin (20.0 g, 0.055 mol), lithium chloride (6.4 g, 0.150 mol), tetrakis(triphenylphosphine)palladium(0) (1.7 g, 0.0015 mol), and dioxane (100 mL) was heated under reflux for 23 h. Additional tetrakis(triphenylphosphine)palladium(0) (1.1 g, 0.0010 mol) was added and heating was continued for 25 h. The mixture was cooled, diluted with EtOAc, and ! N KF (100 mL) was added. The solids were removed by filtration through Celite and the layers were separated. The organic phase was washed with pH 7 phosphate buffer (100 mL), brine (100 mL), dried MgSO4), and concentrated. Purification by flash chromatography (twice; 5-10% EtOAc/hexane) gave 6.44 g (61%) of product as a colorless oil.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 23 h
  3. temperatureheating
  4. temperatureThe mixture was cooled
  5. customThe solids were removed by filtration through Celite
  6. customthe layers were separated
  7. washThe organic phase was washed with pH 7 phosphate buffer (100 mL), brine (100 mL), dried MgSO4), and
  8. concentrationconcentrated
  9. customPurification by flash chromatography (twice

Sources & evidence

ORD record
ord-cca7c6f3a4b4453d984fecd152333a56
Source dataset
uspto-grants-1995_11
Patent number
US05466692

Reaction notes

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