Acetic Acid → Ethyl 2-(methylthio)pyrimidine-5-carboxylate

HRID 1890658Notes

Reaction equation

HRID 1890658 reaction equation
Cl[C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:6][N:5]=[C:4]([S:13][CH3:14])[N:3]=1.C(O)(=O)C>C(O)C.O.[Zn]>[CH3:14][S:13][C:4]1[N:3]=[CH:2][C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:6][N:5]=1

Participants

6

Reactant 2

HCID 176Acetic AcidHCID 800084-Chloro-2-(methylthio)pyrimidine-5-carboxylic acid ethyl ester

Product 1

HCID 10442716Ethyl 2-(methylthio)pyrimidine-5-carboxylateYield 36.1%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Commercially available ethyl 4-chloro-2-(methylthio)pyrimidine-5-carboxylate (5.00 g, 21.5 mmol) was dissolved in ethanol (72 mL) and water (14 mL), and zinc powder (14.0 g, 214 mmol) was added to the solution. Then, the mixture was added with acetic acid (2.95 mL, 51.5 mmol) in three portions, followed by stirring at room temperature for 2 hours. After removing the insoluble material by filtration, the filtrate was concentrated under reduced pressure. The residue was dissolved in chloroform, and the organic layer was separated from the aqueous layer. The organic layer was sequentially washed with water and saturated brine, and dried over anhydrous magnesium sulfate, then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:20) to obtain ethyl 2-(methylthio)pyrimidine-5-carboxylate (1.54 g, 36%).

Workup

  1. customAfter removing the insoluble material
  2. filtrationby filtration
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. dissolutionThe residue was dissolved in chloroform
  5. customthe organic layer was separated from the aqueous layer
  6. washThe organic layer was sequentially washed with water and saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:20)

Sources & evidence

ORD record
ord-9b703c2acdc24debb5adfa3d9060490e
Source dataset
uspto-grants-2013_08
Patent number
US08507484B2

Reaction notes

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