Trimethylsilylacetylene → 5-Chloro-3-((trimethylsilyl)ethynyl)pyridin-2-amine

HRID 490449

Reaction equation

HRID 490449 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4](I)[C:5]([NH2:8])=[N:6][CH:7]=1.[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])#[CH:11].[Cl-].[Li+]>C(N(CC)CC)C.CN(C)C=O.[Cu](I)I>[Cl:1][C:2]1[CH:3]=[C:4]([C:11]#[C:10][Si:12]([CH3:15])([CH3:14])[CH3:13])[C:5]([NH2:8])=[N:6][CH:7]=1

Participants

7

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 433294Lithium ChlorideHCID 110760102-Amino-5-chloro-3-iodopyridine

Product 1

HCID 247294655-Chloro-3-((trimethylsilyl)ethynyl)pyridin-2-amine

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
40 °C

Procedure

A suspension of 2.54 g of 5-chloro-3-iodopyridin-2-ylamine, 2.12 ml of ethynyltrimethylsilane, 0.38 g of copper iodide and 0.47 g of lithium chloride in 7 ml of triethylamine and 75 ml of dimethylformamide is degassed under argon for approximately 15 minutes. 0.408 g of [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) chloride is added to the above suspension. The mixture is heated at around 40° C. for approximately 19 hours and then concentrated to dryness under reduced pressure (13 kPa). The residue is taken up with 50 ml of water, and extracted with three times 100 ml of ethyl acetate. The combined organic phases are dried over magnesium sulfate, filtered, and concentrated to dryness under reduced pressure (13 kPa). The residue is purified by flash chromatography on a silica column [eluent: cyclohexane/ethyl acetate (70/30 by volume)]. 1.63 g of 5-chloro-3-trimethylsilanylethynylpyridin-2-ylamine are obtained in the form of a solid, the characteristics of which are as follows:

Workup

  1. customis degassed under argon for approximately 15 minutes
  2. addition0.408 g of [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) chloride is added to the above suspension
  3. concentrationconcentrated to dryness under reduced pressure (13 kPa)
  4. extractionextracted with three times 100 ml of ethyl acetate
  5. dry with materialThe combined organic phases are dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure (13 kPa)
  8. customThe residue is purified by flash chromatography on a silica column [eluent: cyclohexane/ethyl acetate (70/30 by volume)]

Sources & evidence

ORD record
ord-89142a96ad574f4d82569bd0039d3036
Source dataset
uspto-grants-2009_05
Patent number
US07528147B2

Linked notes

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