Methyl 5-bromopyrimidine-2-carboxylate → HCID 55264616, compound

HRID 1526619Notes

Reaction equation

HRID 1526619 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]([C:8]([O:10][CH3:11])=[O:9])=[N:6][CH:7]=1.[Cu][C:13]#[N:14]>CC(N(C)C)=O>[C:13]([C:2]1[CH:3]=[N:4][C:5]([C:8]([O:10][CH3:11])=[O:9])=[N:6][CH:7]=1)#[N:14]

Participants

4

Reactant 2

HCID 45790831Methyl 5-bromopyrimidine-2-carboxylateHCID 178418546HCID 178418546, compound

Product 1

HCID 55264616HCID 55264616, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
110 °C

Procedure

To a mixture of methyl 5-bromopyrimidine-2-carboxylate (2.30 g, 10.6 mmol) and copper (I) cyanide (1.92 g, 21.4 mmol) in a 100 mL round bottom flask was added DMA (21 mL). The reaction mixture was degassed by bubbling nitrogen through the solution for 5 min. The reaction mixture was heated to 110° C. for 2 d and cooled to room temperature. The reaction mixture was diluted with EtOAc and water and filtered through a glass frit (medium). The filtrate was transferred to a separatory funnel. The aqueous phase was extracted with EtOAc (4×) and the combined organic extracts were washed with brine (1×), dried over MgSO4, filtered, concentrated to give a yellow oil. Purification by flash column chromatography on silica gel (80 g, 5% to 50% EtOAc in heptane) gave methyl 5-cyanopyrimidine-2-carboxylate (0.83 g, 5.08 mmol, 48% yield) as a white solid. LC/MS (ESI+) m/z=164.0 (M+H). Calculated for C7H5N3O2 163.0.

Workup

  1. customThe reaction mixture was degassed
  2. customby bubbling nitrogen through the solution for 5 min
  3. temperaturecooled to room temperature
  4. additionThe reaction mixture was diluted with EtOAc and water
  5. filtrationfiltered through a glass frit (medium)
  6. customThe filtrate was transferred to a separatory funnel
  7. extractionThe aqueous phase was extracted with EtOAc (4×)
  8. washthe combined organic extracts were washed with brine (1×)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customto give a yellow oil
  13. customPurification by flash column chromatography on silica gel (80 g, 5% to 50% EtOAc in heptane)

Sources & evidence

ORD record
ord-01e82352e4094df8adf5610b7a2c21ab
Source dataset
uspto-grants-2015_07
Patent number
US09085576B2

Reaction notes

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