Dichloromethane ethylacetate → HCID 59579884, compound

HRID 2279628Notes

Reaction equation

HRID 2279628 reaction equation
N([O-])=O.[Na+].N[C:6]1[C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:9][N:8]([C:16]2[N:21]=[CH:20][CH:19]=[CH:18][N:17]=2)[N:7]=1.CCOC(C)=O.C(Cl)[Cl:29]>O.Cl.C(Cl)(Cl)Cl.[Cu]Cl>[Cl:29][C:6]1[C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:9][N:8]([C:16]2[N:21]=[CH:20][CH:19]=[CH:18][N:17]=2)[N:7]=1

Participants

8

Reactant 3

HCID 21226138Dichloromethane ethylacetateHCID 23668193Sodium NitriteHCID 59579963HCID 59579963, compound

Product 1

HCID 59579884HCID 59579884, compound

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×HCID 6212ChloroformSolvent2×

Procedure

A solution of sodium nitrite (1.0 g, 15.1 mmol) in 5.0 mL of water is added dropwise to a solution of ethyl 3-amino-1-pyrimidin-2-yl-1H-pyrazole-4-carboxylate (2.7 g, 11.6 mmol) in 18 mL of conc. HCl at −5° C. with stirring. After 1 h at 0° C., the reaction mixture is added dropwise to a suspension of copper (I) chloride (1.8 g, 18.6 mmol) in 18 mL of CHCl3 at RT. After 1 h at RT, water (40 mL) and CHCl3 (40 mL) are added, and the layers are separated. The organic layer is washed once more with water (40 mL), dried (Na2SO4), filtered, and evaporated in vacuo to give a greenish/yellow solid. TLC analysis (70% EtOAc/CH2Cl2) of this crude solid reveals 2 products, which are separated by column chromatography (10% EtOAc/CH2Cl2) to afford ethyl 3-chloro-1-pyrimidin-2-yl-1H-pyrazole-4-carboxylate (Rf≈0.7) as a white solid. The minor, more polar compound ethyl 5-chloro-1-pyrimidin-2-yl-1H-pyrazole-4-carboxylate, Rf≈0.5) is also isolated as a white solid.

Workup

  1. waitAfter 1 h at RT
  2. customthe layers are separated
  3. washThe organic layer is washed once more with water (40 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto give a greenish/yellow solid
  8. customare separated by column chromatography (10% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-c855b6aa39c34210a6bad719638614e4
Source dataset
uspto-grants-2015_09
Patent number
US09133204B2

Reaction notes

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