Dimethylformamide → HCID 21948537, compound

HRID 2214787Notes

Reaction equation

HRID 2214787 reaction equation
I[C:2]1[CH:3]=[N:4][NH:5][C:6]=1[C:7]1[CH:12]=[CH:11][N:10]=[C:9]([S:13][CH3:14])[N:8]=1.[CH3:15][N:16](C=O)C>[C-]#N.[Zn+2].[C-]#N.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:15]([C:2]1[CH:3]=[N:4][NH:5][C:6]=1[C:7]1[CH:12]=[CH:11][N:10]=[C:9]([S:13][CH3:14])[N:8]=1)#[N:16]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 21948419HCID 21948419, compound

Product 1

HCID 21948537HCID 21948537, compound

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

A solution of 4-(4-Iodo-1H-pyrazol-5-yl)-2-(methylthio)pyrimidine (4-2, 710 mg, 2.23 mmol, 1 equiv), zinc cyanide(157 mg, 1.34 mmol, 0.6 equiv), 1,1′-bis(diphenylphosphino)ferrocene (297 mg, 0.54 mmol, 0.24 equiv), and tris (dibenzylideneacetone)dipalladium(0) (204 mg, 0.22 mmol, 0.1 equiv) in DMF (10 mL) was degassed and placed in a 105° C. oil bath. After 1 hour the reaction was concentrated and partitioned between ethyl acetate and saturated sodium bicarbonate solution. The organic layer was washed with brine, dried over magnesium sulfate and concentrated. The resulting oil was purified by chromatographed. Elution with 5–25% EtOAc/CH2Cl2 gave 4-(4-cyano-1H-pyrazol-5-yl)-2-(methylthio)pyrimidine (4-3) as a tan solid. LRMS m/z: Calc'd for C9H7N5S (M+H) 318.1. found 318.0.

Workup

  1. customplaced in a 105° C.
  2. concentrationAfter 1 hour the reaction was concentrated
  3. custompartitioned between ethyl acetate and saturated sodium bicarbonate solution
  4. washThe organic layer was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customThe resulting oil was purified
  8. customby chromatographed
  9. washElution with 5–25% EtOAc/CH2Cl2

Sources & evidence

ORD record
ord-5f2bb7338de847ef93b0243cb1cf825d
Source dataset
uspto-grants-2006_09
Patent number
US07109204B2

Reaction notes

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