Oxalyl chloride → Quinoline-6-carbonyl chloride

HRID 596134Notes

Reaction equation

HRID 596134 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][C:7]([C:11]([OH:13])=O)=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.C(Cl)(=O)C([Cl:17])=O>CN(C=O)C.O1CCOCC1>[N:1]1[C:10]2[C:5](=[CH:6][C:7]([C:11]([Cl:17])=[O:13])=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 825716-Quinolinecarboxylic acid

Product 1

HCID 12391963Quinoline-6-carbonyl chloride

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 312751,4-DioxaneSolvent

Procedure

Under nitrogen, a 1 L round bottom flask, equipped with septum and drying tube attached to a gas scrubber setup, was charged with 25.4 g (146.5 mmol) quinoline-6-carboylic acid. 1,4-Dioxane (250 mL) was added along with 10 drops of DMF. Inside a glovebox, oxalyl chloride (25.1 g, 197.8 mmol, 1.35 eq) was weighed into a septum vial. The vial was closed, removed from the glovebox, and the weighed oxalyl chloride was added, under nitrogen, to the reaction, in portions, via syringe. The reaction was stirred until most of the gas development ceased. The reaction remained stirring at room temperature overnight. The volatiles were removed using a rotary evaporator. Trace HCl was removed by addition of several aliquots of dry toluene, which were consecutively evaporated using the rotary evaporator. The final product was obtained in form of a colorless to slightly yellow powder (28.0 g, 146.4 mmol, 100%). 1H-NMR: (500 MHz, CDCl3) δ 9.35 (dd, J=5.2, 1.5 Hz, 1H), 9.09 (d, J=8.5 Hz, 1H), 9.09 (d, J=9.0 Hz, 1H), 9.01 (d, J=2.0 Hz, 1H), 8.64 (dd, J=9.1, 2.0 Hz, 1H), 8.14 (dd, J=8.4, 5.2 Hz, 1H); 13C-NMR (126 MHz, CDCl3) δ 122.92, 123.90, 128.21, 133.44, 133.79, 134.55, 140.95, 146.44, 147.11, 166.69.

Workup

  1. customUnder nitrogen, a 1 L round bottom flask, equipped with septum
  2. customdrying tube
  3. customThe vial was closed
  4. customremoved from the glovebox
  5. additionthe weighed oxalyl chloride was added, under nitrogen, to the reaction, in portions, via syringe
  6. stirringThe reaction remained stirring at room temperature overnight
  7. customThe volatiles were removed
  8. customa rotary evaporator
  9. customTrace HCl was removed by addition of several aliquots of dry toluene, which
  10. customwere consecutively evaporated
  11. customthe rotary evaporator

Sources & evidence

ORD record
ord-9486469da1764d8d9b8aa44286b714d6
Source dataset
uspto-grants-2016_01
Patent number
US09246108B2

Reaction notes

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