Triethylamine → 2-Amino-3-cyano-5-(trimethylsilylethynyl)pyrazine

HRID 440900Notes

Reaction equation

HRID 440900 reaction equation
[NH2:1][C:2]1[C:7]([C:8]#[N:9])=[N:6][C:5](Br)=[CH:4][N:3]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13].C(N(CC)CC)C>C(#N)C.[Cu](I)I.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>[NH2:1][C:2]1[C:7]([C:8]#[N:9])=[N:6][C:5]([C:16]#[C:15][Si:12]([CH3:14])([CH3:13])[CH3:11])=[CH:4][N:3]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 110526113-Amino-6-bromopyrazine-2-carbonitrile

Product 1

HCID 153352712-Amino-3-cyano-5-(trimethylsilylethynyl)pyrazine

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

A solution of 3.0 grams (0.015 mole) of 2-amino-3-cyano-5-bromopyrazine and 2.1 grams (0.021 mole) of trimethylsilylacetylene in 50 mL of acetonitrile is stirred, and 10.6 mL of triethylamine, 0.13 gram of copper iodide, and 0.29 gram of bis(triphenylphosphine)palladium(II) chloride are added in order. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 20 hours. The reaction mixture is warmed to 70° C., where it is stirred for about 7.5 hours. After this time, the reaction mixture is concentrated under reduced pressure to a residue. The residue is dissolved in ethyl acetate, and the solution is washed with 50 mL of aqueous, dilute hydrochloric acid. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel. Elution is accomplished using tetrahydrofuran/methylene chloride combinations. The product-containing fractions are combined and concentrated under reduced pressure, yielding 2-amino-3-cyano-5-(trimethylsilylethynyl)pyrazine.

Workup

  1. additionUpon completion of addition
  2. temperatureThe reaction mixture is warmed to 70° C.
  3. stirringwhere it is stirred for about 7.5 hours
  4. concentrationAfter this time, the reaction mixture is concentrated under reduced pressure to a residue
  5. dissolutionThe residue is dissolved in ethyl acetate
  6. washthe solution is washed with 50 mL of aqueous, dilute hydrochloric acid
  7. dry with materialThe organic layer is dried with magnesium sulfate
  8. filtrationfiltered
  9. concentrationThe filtrate is concentrated under reduced pressure to a residue
  10. washElution
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-60c7bc983ef44322ae3c7c95a37bb877
Source dataset
uspto-grants-1996_05
Patent number
US05521190

Reaction notes

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