Triethylamine → 5-Bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-amine

HRID 1959382Notes

Reaction equation

HRID 1959382 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].Br[C:8]1[C:9]([NH2:15])=[N:10][CH:11]=[C:12]([Br:14])[N:13]=1.C(N(CC)CC)C>CN(C=O)C.CCOC(C)=O.O.[Cu]I.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>[Br:14][C:12]1[N:13]=[C:8]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[C:9]([NH2:15])=[N:10][CH:11]=1

Participants

9

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 6200042-Amino-3,5-dibromopyrazine

Product 1

HCID 533931895-Bromo-3-((trimethylsilyl)ethynyl)pyrazin-2-amineYield 78.6%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

(Trimethylsilyl)acetylene (1.845 g, 2.655 mL, 18.78 mmol) was added dropwise to a solution of 3,5-dibromopyrazin-2-amine (5 g, 19.77 mmol), triethylamine (10.00 g, 13.77 mL, 98.85 mmol), Copper(I) iodide (451.7 mg, 2.372 mmol) and Pd(PPh3)4(1.142 g, 0.9885 mmol) in DMF (25.00 mL) and the resulting solution stirred at ambient temperature for 30 minutes. The reaction was diluted with EtOAc and water and the layers separated. The aqueous layer was extracted further with EtOAc and the combined organics washed with water, dried (MgSO4) and concentrated in vacuo. The mixture was purified on silica gel by flash column chromatography (0-15% EtOAc/Petrol) to afford the product as a yellow solid (3.99 g, 75% Yield). 1H NMR (400.0 MHz, DMSO) d 0.30 (s, 9H), 8.06 (s, 1H) ppm; MS (ES+) 271.82

Workup

  1. customthe layers separated
  2. extractionThe aqueous layer was extracted further with EtOAc
  3. washthe combined organics washed with water
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customThe mixture was purified on silica gel by flash column chromatography (0-15% EtOAc/Petrol)

Sources & evidence

ORD record
ord-bfdc9ebd9f3e4fc286a8230f06155aa3
Source dataset
uspto-grants-2013_04
Patent number
US08410112B2

Reaction notes

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