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

HRID 81373Notes

Reaction equation

HRID 81373 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.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

8

Reactant 3

HCID 6228DimethylformamideHCID 66111TrimethylsilylacetyleneHCID 6200042-Amino-3,5-dibromopyrazine

Product 1

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

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 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 1 (5 g, 19.77 mmol) in DMF (25 mL) 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) were then added and the resulting solution stirred at RT for 30 minutes. The reaction mixture was diluted with EtOAc and water and the layers separated. The aqueous layer was extracted further with EtOAc and the combined organic layers washed with water, dried (MgSO4) and concentrated in vacuo. The residue was purified by column chromatography eluting with 15% EtOAc/Petroleum ether to give the product as a yellow solid (3.99 g, 75% Yield). 1H NMR (400.0 MHz, DMSO) δ 0.30 (9H, s), 8.06 (1H, s); MS (ES+) 271.82

Workup

  1. additionwere then added
  2. customthe layers separated
  3. extractionThe aqueous layer was extracted further with EtOAc
  4. washthe combined organic layers washed with water
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography
  8. washeluting with 15% EtOAc/Petroleum ether

Sources & evidence

ORD record
ord-16720f2c19f14321ad76598f701659f4
Source dataset
uspto-grants-2014_09
Patent number
US08846686B2

Reaction notes

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