Water → 3-((Trimethylsilyl)ethynyl)pyridin-2-amine

HRID 1891509Notes

Reaction equation

HRID 1891509 reaction equation
[NH2:1][C:2]1[C:7](Br)=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11].C(N(CC)C(C)C)(C)C.O>CN1CCCC1=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH3:9][Si:10]([C:13]#[C:14][C:7]1[C:2]([NH2:1])=[N:3][CH:4]=[CH:5][CH:6]=1)([CH3:12])[CH3:11]

Participants

8

Reactant 4

HCID 962WaterHCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 8177002-Amino-3-bromopyridine

Product 1

HCID 574756663-((Trimethylsilyl)ethynyl)pyridin-2-amineYield 94.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 2-amino-3-bromopyridine (5.72 g, 33.1 mmol) in N-methylpyrrolidinone (120 mL) were added trimethylsilyl acetylene (9.36 mL, 66.2 mmol), tetrakis(triphenylphosphine)palladium (0) (1.91 g, 1.66 mmol), copper (I) iodide (630 mg, 3.31 mmol) and N,N-diisopropylethylamine (11.5 mL, 66.2 mmol) at room temperature, which was stirred under nitrogen atmosphere for 6 hours at 70° C. Water was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under a reduced pressure. The residue was purified by silica gel column chromatography (heptane:ethyl acetate=2:1) to obtain the title compound (5.94 g, 94%).

Workup

  1. extractionwas then extracted with ethyl acetate
  2. washThe organic layer was washed with water and saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customthe solvent was evaporated under a reduced pressure
  5. customThe residue was purified by silica gel column chromatography (heptane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-b49d322238904ea58009a2e56c28f71e
Source dataset
uspto-grants-2013_08
Patent number
US08507530B2

Reaction notes

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