Thionyl Chloride → HCID 59293381, compound

HRID 1914605Notes

Reaction equation

HRID 1914605 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([OH:10])=O)[C:5]([Cl:11])=[CH:4][N:3]=1.O=S(Cl)Cl.[C:16]([O:22][CH2:23][CH3:24])(=[O:21])[CH2:17]C([O-])=O.[K+].[Cl-].[Mg+2].[Cl-]>CN(C=O)C.C(#N)C.C(N(CC)CC)C>[Cl:1][C:2]1[CH:7]=[C:6]([C:8](=[O:10])[CH2:17][C:16]([O:22][CH2:23][CH3:24])=[O:21])[C:5]([Cl:11])=[CH:4][N:3]=1

Participants

8

Reactant 4

HCID 24386Thionyl ChlorideHCID 27360872,5-Dichloroisonicotinic acidHCID 3446434Potassium ethyl malonateHCID 5360315Magnesium Chloride

Product 1

HCID 59293381HCID 59293381, compound

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 2,5-dichloropyridine-4-carboxylic acid (2 g) and SOCl2 (10 ml) and 1 drop of DMF were heated under reflux for 2 h, and all SOCl2 and DMF removed under reduced pressure to give the crude acid chloride as the remaining residue. Separately, a suspension of potassium ethyl malonate (5 g) in acetonitrile (100 ml) was cooled to 0° C., magnesium chloride (4 g) and triethylamine (4 ml) were added, the ice bath removed and the reaction stirred at RT for 3 h. A solution of the crude acid chloride in DCM (25 ml) was carefully added to the malonate slurry and the resulting mixture stirred at RT overnight. Aqueous HCl (100 ml, 1M) was added and stiffing continued for 1 h. This mixture was then extracted with diethyl ether (200 ml×3), the organic layer washed with saturated sodium bicarbonate (200 ml×2) and brine (200 ml), dried over anhydrous magnesium sulfate, filtered and concentrated. The title compound was obtained as light yellow oil (1.6 g) which was on-reacted without further purification and without further characterization other than ascertaining that the compound was one spot by tlc with the expected molecular weight (M−1) of 260.

Workup

  1. temperaturewere heated
  2. temperatureunder reflux for 2 h
  3. customall SOCl2 and DMF removed under reduced pressure
  4. customto give the crude acid chloride as the remaining residue
  5. customthe ice bath removed
  6. additionA solution of the crude acid chloride in DCM (25 ml) was carefully added to the malonate slurry
  7. stirringthe resulting mixture stirred at RT overnight
  8. additionAqueous HCl (100 ml, 1M) was added
  9. waitstiffing continued for 1 h
  10. extractionThis mixture was then extracted with diethyl ether (200 ml×3)
  11. washthe organic layer washed with saturated sodium bicarbonate (200 ml×2) and brine (200 ml)
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-c89714c905be47429d7db29b402245a6
Source dataset
uspto-grants-2013_12
Patent number
US08614212B2

Reaction notes

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