Ethyl 2,6-dichloro-5-nitropyrimidine-4-carboxylate → Ethyl 5-amino-2-chloropyrimidine-4-carboxylate

HRID 1185385Notes

Reaction equation

HRID 1185385 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:5]([N+:13]([O-])=O)=[C:4](Cl)[N:3]=1.[O-2].[Mg+2]>[Pd].O1CCOCC1>[NH2:13][C:5]1[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[N:7][C:2]([Cl:1])=[N:3][CH:4]=1

Participants

5

Reactant 2

HCID 2761044Ethyl 2,6-dichloro-5-nitropyrimidine-4-carboxylateHCID 6850729Magnesium monoxide

Product 1

HCID 12258910Ethyl 5-amino-2-chloropyrimidine-4-carboxylateYield 55%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

In a Parr hydrogenator, ethyl 2,6-dichloro-5-nitropyrimidine-4-carboxylate (2.16 g, 8.12 mmol), 10% Pd/C (2.0 g, 0.94 mmol), magnesium monoxide (1.60 g, 39.7 mmol) and 1,4-dioxane (100 mL) were charged. The hydrogenation was allowed to go at room temperature under 50-60 psi for 2 days while monitored by LCMS. The reaction mixture was filtered through Celite and washed with methanol. The filtrate was concentrated and purified via flash chromatography eluting with 50 to 100% ethyl acetate in heptane to give ethyl 5-amino-2-chloropyrimidine-4-carboxylate (0.90 g, 55%).

Workup

  1. filtrationThe reaction mixture was filtered through Celite
  2. washwashed with methanol
  3. concentrationThe filtrate was concentrated
  4. custompurified via flash chromatography
  5. washeluting with 50 to 100% ethyl acetate in heptane

Sources & evidence

ORD record
ord-c63cd1facfe646fd9e80e0a7e2cad924
Source dataset
uspto-grants-2014_03
Patent number
US08669361B2

Reaction notes

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