Triethylamine → HCID 89996041, compound

HRID 1480859Notes

Reaction equation

HRID 1480859 reaction equation
Br[C:2]1[C:3]([C:10]([O:12][CH3:13])=[O:11])=[N:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=1.C(N(CC)CC)C.[C:21]([CH:23]1[CH2:25][CH2:24]1)#[CH:22]>CN(C=O)C.C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:23]1([C:21]#[C:22][C:2]2[C:3]([C:10]([O:12][CH3:13])=[O:11])=[N:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=2)[CH2:25][CH2:24]1

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 138823CyclopropylacetyleneHCID 2794729Methyl 5-bromo-2-(methylsulfanyl)pyrimidine-4-carboxylate

Product 1

HCID 89996041HCID 89996041, compoundYield 86.2%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Methyl 5-bromo-2-(methylthio)pyrimidine-4-carboxylate (639 mg, 2.43 mmole) was dissolved in DMF (6 mL) and triethylamine (1.37 mL) was added. To the solution was added ethynylcyclopropane (287 uL, 3.40 mmole), followed by copper (I) iodide (22.4 mg 0.115 mmole) and bis(triphenylphosphine)palladium dichloride (85.4 mg 0.115 mmole). The reaction was placed under nitrogen at heated at 80° C. for 3.25 hours. The reaction was diluted with ethyl acetate (75 mL) and the solution was washed with water (25 mL). The organic layer was washed again with water (2×25 mL), brine, dried and concentrated in vacuo. The residue was purified by silica gel column chromatography eluting with 5-10% ethyl acetate in cyclohexanes to afford the title compound (520 mg, 86%). Taken on directly to the next step.

Workup

  1. washthe solution was washed with water (25 mL)
  2. washThe organic layer was washed again with water (2×25 mL), brine
  3. customdried
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel column chromatography
  6. washeluting with 5-10% ethyl acetate in cyclohexanes

Sources & evidence

ORD record
ord-4627a45e072b49af8285794ed9595af0
Source dataset
uspto-grants-2016_08
Patent number
US09409907B2

Reaction notes

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