Dimethylformamide → HCID 86709874, compound

HRID 2206983Notes

Reaction equation

HRID 2206983 reaction equation
[Cl:1][C:2]1[C:7]([Cl:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=2)[N:5]=[C:4]([C:16]([OH:18])=O)[CH:3]=1.S(Cl)([Cl:21])=O.CN(C)C=O.CN(C1C=CC=CN=1)C>C1(C)C=CC=CC=1.CO>[Cl:1][C:2]1[C:7]([Cl:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=2)[N:5]=[C:4]([C:16]([Cl:21])=[O:18])[CH:3]=1

Participants

7

Reactant 4

HCID 6228Dimethylformamide2×HCID 218852-DimethylaminopyridineHCID 24386Thionyl Chloride2×HCID 86709872HCID 86709872, compound

Product 1

HCID 86709874HCID 86709874, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

To a mixture of 4,5-dichloro-6-(4-chlorophenyl)picolinic acid (3.00 g, 9.9 mmol) in toluene (25 mL) was added thionyl chloride (1.08 mL, 14.9 mmol) and dimethylformamide (0.04 mL, 0.5 mmol). Reaction mixture was heated at 80° C. for 2.5 h. HPLC analysis of the reaction mixture treated with methanol and dimethylaminopyridine indicated starting material remaining. Reaction mixture was allowed to cool to room temperature and additional thionyl chloride (0.5 mL, 6.9 mmol) and dimethylformamide (0.04 mL, 0.5 mmol) were added. Reaction was heated at 80° C. for an additional 2 h. Reaction was allowed to cool to room temperature and concentrated under reduced pressure to provide a white solid. Toluene (40 mL) was added to dissolve the solid and concentrated under reduced pressure and then this process was performed a second time. 4,5-Dichloro-6-(4-chlorophenyl)picolinoyl chloride was isolated as a white solid (3.05 g, 96% yield). 1H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H), 7.79-7.72 (m, 2H), 7.53-7.46 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 168.66, 157.63, 146.48, 145.44, 136.35, 135.10, 134.28, 131.04, 128.63, 124.90. LRMS: Calcd. for C12H5Cl4NO, 320.91. Found: m/z=257 (M+-COCl), 222, 207, 186, 151.

Workup

  1. customReaction mixture
  2. customReaction mixture
  3. temperatureto cool to room temperature
  4. customReaction
  5. temperaturewas heated at 80° C. for an additional 2 h
  6. customReaction
  7. temperatureto cool to room temperature
  8. concentrationconcentrated under reduced pressure
  9. customto provide a white solid
  10. dissolutionto dissolve the solid
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ab4cab779ea74455aa774917188af0e0
Source dataset
uspto-grants-2016_06
Patent number
US09376388B2

Reaction notes

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