Triphenylphosphine → 4-Phenoxy-6-prop-1-yn-1-ylpyrimidin-5-amine

HRID 1926114Notes

Reaction equation

HRID 1926114 reaction equation
I[C:2]1[C:7]([NH2:8])=[C:6]([O:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[N:5]=[CH:4][N:3]=1.[C:16]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:21]=CC=C[CH:17]=1.[F-].[K+].C(=O)([O-])O.[Na+]>CN(C)C=O.C(N(CC)CC)C.C[Si](C)(C)C#CC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[O:9]([C:6]1[C:7]([NH2:8])=[C:2]([C:17]#[C:16][CH3:21])[N:3]=[CH:4][N:5]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

10

Reactant 4

HCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 522689Potassium FluorideHCID 860847854-Iodo-6-phenoxy-5-pyrimidinamine

Product 1

HCID 568510544-Phenoxy-6-prop-1-yn-1-ylpyrimidin-5-amineYield 730%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolventHCID 803631-(Trimethylsilyl)prop-1-yneSolvent

Conditions

Temperature
60 °C

Procedure

4-Iodo-6-phenoxypyrimidin-5-amine (5.00 g) was dissolved in a mixed solvent of N,N-dimethylformamide (100 mL)/triethylamine (50 mL), and 1-(trimethylsilyl)-1-propyne (3.3 mL), trans-dichlorobis(triphenylphosphine)palladium(II) (557.7 mg), triphenylphosphine (421.1 mg), copper(I) iodide (303.0 mg) and potassium fluoride (1.29 g) were sequentially added. The mixture was stirred at 60° C. under an argon stream for 16 hrs. The reaction mixture was treated with saturated aqueous sodium hydrogen carbonate solution and extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent, hexane:ethyl acetate=80:20→50:50) to give the title compound (2.64 g) as a orange solid.

Workup

  1. additionwere sequentially added
  2. extractionextracted with diethyl ether
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was separated
  7. custompurified by silica gel column chromatography (eluent, hexane:ethyl acetate=80:20→50:50)

Sources & evidence

ORD record
ord-e7ff8472a19c4b34a1fb10e315f96b46
Source dataset
uspto-grants-2012_05
Patent number
US08178543B2

Reaction notes

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