Oxalyl chloride → 3-Chloro-7,8-dihydroquinolin-5(6H)-one

HRID 1591253Notes

Reaction equation

HRID 1591253 reaction equation
C(Cl)(=O)C(Cl)=O.[Cl:7][C:8](=[CH:11]Cl)[CH:9]=O.[NH2:13][C:14]1[CH2:19][CH2:18][CH2:17][C:16](=[O:20])[CH:15]=1>C(Cl)Cl.CN(C)C=O.C([O-])(O)=O.[Na+]>[Cl:7][C:8]1[CH:9]=[N:13][C:14]2[CH2:19][CH2:18][CH2:17][C:16](=[O:20])[C:15]=2[CH:11]=1

Participants

7

Reactant 3

HCID 65578Oxalyl chlorideHCID 788923-Aminocyclohex-2-en-1-oneHCID 1505162,3-Dichloro-2-propenal

Product 1

HCID 109976543-Chloro-7,8-dihydroquinolin-5(6H)-one

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

Chloromalondialdehyde (19 grams, 0.178 mol) was suspended in methylene chloride (100 ml) with dry dimethylformamide (DMF) (2.5 ml). This was mechanically stirred under a nitrogen atmosphere while a solution of oxalyl chloride (23.7 grams/16.3 ml, 0.185 mol) in methylene chloride (50 ml) was added dropwise over 20 minutes. The reaction mixture at first started to warm from 22° to 28°, but as the evolution of gases increased the temperature fell to 18°. The reaction was stirred at room temperature and was followed by thin layer chromatography (ethyl acetate/hexanes, 1:1) until conversion to 2,3-dichloroacrolein was complete. A solution of 1-amino-cyclohexen-3-one (19.85 grams, 0.18 mol) in DMF (125 ml) was added dropwise and the reaction was heated to 70° C. overnight. The reaction mixture was cooled to room temperature, diluted with saturated NaHCO3, and twice extracted with ethyl acetate (400 ml and 200 ml). The combined organic layers were washed with water (3×) and brine (1×). The organic solution was stirred with MgSO4 and decolorizing carbon (Darco (trademark)); then filtered through Super Cel (trademark)) and concentrated to a brown solid. Yield 21 grams (65%); mp 90°-91° C. NMR (CDCl3, 300 MHz) δ8.6 (d, 1), 8.24 (d, 1), 3.1 (t, 2), 2.7 (m, 2), 2.15 (m, 2).

Workup

  1. additionwas added dropwise over 20 minutes
  2. temperatureto warm from 22° to 28°
  3. temperatureas the evolution of gases increased the temperature
  4. customfell to 18°
  5. temperaturethe reaction was heated to 70° C. overnight
  6. temperatureThe reaction mixture was cooled to room temperature
  7. extractiontwice extracted with ethyl acetate (400 ml and 200 ml)
  8. washThe combined organic layers were washed with water (3×) and brine (1×)
  9. stirringThe organic solution was stirred with MgSO4
  10. filtrationthen filtered through Super Cel (trademark)) and
  11. concentrationconcentrated to a brown solid

Sources & evidence

ORD record
ord-3bb40f4bc35c4c28963ca95bd3f9eb45
Source dataset
uspto-grants-1993_04
Patent number
US05206367

Reaction notes

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