Triethylamine → HCID 58084367, compound

HRID 2174655Notes

Reaction equation

HRID 2174655 reaction equation
[C:1]1([C:7]#[CH:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:10]1[C:11]([NH2:17])=[N:12][CH:13]=[C:14]([Br:16])[N:15]=1.C(N(CC)CC)C>CN(C=O)C.CCOC(C)=O.[Cl-].[Na+].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:16][C:14]1[N:15]=[C:10]([C:8]#[C:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:11]([NH2:17])=[N:12][CH:13]=1

Participants

9

Reactant 3

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 6200042-Amino-3,5-dibromopyrazine

Product 1

HCID 58084367HCID 58084367, compoundYield 70.6%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
120 °C

Procedure

Phenylacetylene (969.2 mg, 1.044 mL, 9.490 mmol) was added dropwise to a solution of 3,5-dibromopyrazin-2-amine (2 g, 7.908 mmol), triethylamine (8.002 g, 11.02 mL, 79.08 mmol), copper (I) iodide (180.7 mg, 0.9490 mmol) and Pd(PPh3)4 (456.9 mg, 0.3954 mmol) in DMF (24 mL) and the resulting solution heated at 120° C. for 10 minutes. The reaction mixture was cooled to ambient temperature and diluted with EtOAc (20 mL) and 1 MHCl/brine (10 mL/10 mL) and the layers separated. The aqueous layer was extracted with ethyl acetate (2×20 mL) and combined organics washed with brine (2×20 mL), dried over (MgSO4) and concentrated in vacuo. The residue was purified by column chromatography (ISCO Companion™, 80 g column, eluting with 0 to 50% EtOAc/Petroleum Ether, loaded in DCM) to give the sub-tile compound as an off-white solid (1.53 g, 70%). 1H NMR (400.0 MHz, DMSO) δ 7.04 (br s, 2H), 7.46-7.50 (m, 3H), 7.75-7.77 (m, 2H) and 8.13 (s, 1H) ppm; (ES+) 275.8.

Workup

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. customthe layers separated
  3. extractionThe aqueous layer was extracted with ethyl acetate (2×20 mL)
  4. washcombined organics washed with brine (2×20 mL)
  5. dry with materialdried over (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography (ISCO Companion™, 80 g column, eluting with 0 to 50% EtOAc/Petroleum Ether, loaded in DCM)

Sources & evidence

ORD record
ord-feed8f6fae7b4896b08d232ae00f3c43
Source dataset
uspto-grants-2015_06
Patent number
US09062008B2

Reaction notes

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