Oxalyl chloride → Methyl 5-bromopyrimidine-4-carboxylate

HRID 1919626Notes

Reaction equation

HRID 1919626 reaction equation
[Br:1][C:2]1[C:3]([C:8]([OH:10])=[O:9])=[N:4][CH:5]=[N:6][CH:7]=1.[C:11](Cl)(=O)C(Cl)=O>C(Cl)Cl.CN(C=O)C>[CH3:11][O:9][C:8]([C:3]1[C:2]([Br:1])=[CH:7][N:6]=[CH:5][N:4]=1)=[O:10]

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 213292005-Bromopyrimidine-4-carboxylic acid

Product 1

HCID 45790077Methyl 5-bromopyrimidine-4-carboxylateYield 39%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

5-bromopyrimidine-4-carboxylic acid (prepared according to the procedure described in U.S. Pat. No. 4,110,450) (1.0 eq, 6.14 g, 30.2 mmol) was suspended in CH2Cl2 (100 ml). Oxalylchloride (1.1 eq, 2.9 ml, 33.0 mmol) was added followed by 2 drops of DMF. The mixture was stirred at room temperature overnight and the volatiles were removed in vacuo. The residue was taken in MeOH (50 ml) and heated. After evaporation of MeOH in vacuo the compound was dissolved in CH2Cl2 and poured on a prepacked silica gel column. The material was eluted using 20% Ethyl acetate in hexanes. Evaporation of the solvent provided methyl-5-bromopyrimidine-4-carboxylate as a light orange crystalline solid (2.54 g, 39% yield). LCMS (ES): 95% pure, m/z 217 [M]+; 219 [M+2]+; 1H NMR (CDCl3, 400 MHz) δ 4.04 (s, 3H), 9.02 (s, 1H), 9.21 (s, 1H) ppm.

Workup

  1. customthe volatiles were removed in vacuo
  2. temperatureheated
  3. customAfter evaporation of MeOH in vacuo the compound
  4. dissolutionwas dissolved in CH2Cl2
  5. additionpoured on a prepacked silica gel column
  6. washThe material was eluted
  7. customEvaporation of the solvent

Sources & evidence

ORD record
ord-13e8ffe0ba1d4aae8a111e786632ed3c
Source dataset
uspto-grants-2012_05
Patent number
US08168651B2

Reaction notes

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