Dichloromethane → Ethyl 4,6-dichloropyridine-3-carboxylate

HRID 2174223Notes

Reaction equation

HRID 2174223 reaction equation
O[C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:6][N:5]=[C:4](O)[CH:3]=1.[Cl-:14].[Cl-:15].[Ca+2].C(Cl)Cl>O(Cl)Cl.[P+5].O>[Cl:14][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:6][N:5]=[C:4]([Cl:15])[CH:3]=1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 5284359Calcium ChlorideHCID 178469844HCID 178469844, compound

Product 1

HCID 600045Ethyl 4,6-dichloropyridine-3-carboxylate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 178479711HCID 178479711, compoundSolvent

Procedure

(Wallace, E., et. al., ibid.) A stirred suspension of compound ii (1.40 g, 7.67 mmol) in phosphorus (V) oxychloride (15 mL) was heated to 110° C. for 2.5 h with a guard tube (CaCl2) fitted. The reaction mixture was cooled to room temperature, reduced in vacuo and the resulting dark brown residue taken up in a small volume of DCM (˜5 mL) and transferred dropwise onto a slurry of ice in water (250 mL) whilst stirring vigorously. The aqueous mixture was extracted with EtOAc (3×100 mL), the organic extracts combined, dried (MgSO4) and evaporated to dryness to afford the crude product as an orange gum. Column chromatography (SiO2), eluting with 15:1 Hexanes-EtOAc, afforded compound iii. (1.33 g, 6.14 mmol, 79%) as a colourless oil; [M+H]+ m/z=220.0.

Workup

  1. customfitted
  2. extractionThe aqueous mixture was extracted with EtOAc (3×100 mL)
  3. dry with materialdried (MgSO4)
  4. customevaporated to dryness
  5. customto afford the crude product as an orange gum
  6. washColumn chromatography (SiO2), eluting with 15:1 Hexanes-EtOAc

Sources & evidence

ORD record
ord-2b4f263645504360b6a79a268430cc71
Source dataset
uspto-grants-2015_06
Patent number
US09060515B2

Reaction notes

Loading…