Carbon Dioxide → 2,4-Dichloronicotinic Acid

HRID 1159459Notes

Reaction equation

HRID 1159459 reaction equation
C([N-]C(C)C)(C)C.[Li+].[Cl:9][C:10]1[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][N:11]=1.[C:17](=[O:19])=[O:18]>C1COCC1>[Cl:9][C:10]1[N:11]=[CH:12][CH:13]=[C:14]([Cl:16])[C:15]=1[C:17]([OH:19])=[O:18]

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 335152,4-DichloropyridineHCID 2724682Lithium diisopropylamide

Product 1

HCID 105838872,4-Dichloronicotinic AcidYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Lithium diisopropylamide (2M in heptane/THF/benzene, 16.7 mL) was treated dropwise with 2,4-dichloropyridine (5 g, 33.8 mmol) at −78° C. in THF (25 mL). The mixture was stirred at −78° C. for 2 hours, treated with excess dry ice, allowed to warm up to room temperature, and partitioned between diethyl ether and an equal volume of 10% aqueous KOH. The basic extract was neutralized with 10% HCl and extracted with diethyl ether. The ethereal extract was dried (Na2SO4), filtered, and the filtrate wasconcentrated under reduced pressure to provide 9.5 g (70% yield) of the title compound. 1H NMR (300 MHz, DMSO-D6) δ ppm 3.32 (s, 1H), 7.74 (d, J=5.42 Hz,1H), 8.47 (d, J=5.42 Hz,1H).

Workup

  1. temperatureto warm up to room temperature
  2. custompartitioned between diethyl ether
  3. extractionThe basic extract
  4. extractionextracted with diethyl ether
  5. extractionThe ethereal extract
  6. dry with materialwas dried (Na2SO4)
  7. filtrationfiltered

Sources & evidence

ORD record
ord-f8c83309b4234578945c8e9f1fa7bf14
Source dataset
uspto-grants-2010_10
Patent number
US07812166B2

Reaction notes

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