Triethylamine → 2-Amino-3-cyano-4-methyl-5-(trimethylsilylethynyl)pyridine

HRID 1078241Notes

Reaction equation

HRID 1078241 reaction equation
[NH2:1][C:2]1[C:7]([C:8]#[N:9])=[C:6]([CH3:10])[C:5](I)=[CH:4][N:3]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14].C(N(CC)CC)C>C(#N)C.[Cu]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])=[C:6]([CH3:10])[C:5]([C:17]#[C:16][Si:13]([CH3:15])([CH3:14])[CH3:12])=[CH:4][N:3]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 113912652-Amino-5-iodo-4-methylnicotinonitrile

Product 1

HCID 197071982-Amino-3-cyano-4-methyl-5-(trimethylsilylethynyl)pyridine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

A solution of 5.1 grams (0.020 mole) of 2-amino-3-cyano-5-iodo-4-methylpyridine (prepared as in Step E of Example 9) and 4.2 mL (0.030 mole) of trimethylsilylacetylene in 40 mL of acetonitrile is stirred, and 10.5 mL (0.078 mole) of triethylamine, 0.1 gram of copper(I) iodide, and 0.3 gram of bis(triphenyl-phosphine)palladium(11) chloride are added in order. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 20 hours and then is warmed to 70° C., where it stirred for about 7.5 hours. The reaction is monitored by thin layer chromatography. Upon completion of the reaction, 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, yielding 2-amino-3-cyano-4-methyl-5-(trimethylsilylethynyl)pyridine.

Workup

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

Sources & evidence

ORD record
ord-d4718eb9a0dd4473aa3d4762932fa3a4
Source dataset
uspto-grants-1996_08
Patent number
US05547954

Reaction notes

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