Dimethyl acetylenedicarboxylate → 2-(Methoxycarbonyl)-4-oxo-6,8-dichloro-7-methylquinoline

HRID 890383Notes

Reaction equation

HRID 890383 reaction equation
[Cl:1][C:2]1[C:7]([NH2:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH3:10].[C:11]([C:17](OC)=[O:18])#[C:12][C:13]([O:15][CH3:16])=[O:14]>CO>[CH3:16][O:15][C:13]([C:12]1[CH2:11][C:17](=[O:18])[C:6]2[C:7](=[C:2]([Cl:1])[C:3]([CH3:10])=[C:4]([Cl:9])[CH:5]=2)[N:8]=1)=[O:14]

Participants

4

Reactant 2

HCID 12980Dimethyl acetylenedicarboxylateHCID 882822,4-Dichloro-m-toluidine

Product 1

HCID 684344222-(Methoxycarbonyl)-4-oxo-6,8-dichloro-7-methylquinolineYield 90.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 2,6-dichloro-3-aminotoluene (20.5 g, 0.11 mol) in methanol (300 mL) was added dimethyl acetylenedicarboxylate (15 mL, 0.12 mol) and the reaction mixture was refluxed for 2 hours. The reaction mixture was concentrated under reduced pressure to a yellow solid. Diphenyl ether (350 mL) was heated to 230–240° C., and the yellow solid was added to it. The temperature was maintained at 230–240° C. for 20 minutes and the reaction mixture was cooled slowly to ambient temperature and diluted with petroleum ether (1 L). The solid was filtered and washed with hot ethyl acetate to afford a brown solid, 2-(methoxycarbonyl)-4-oxo-6,8-dichloro-7-methylquinoline (28.5 g, 85%); NMR (CDCl3) 2.62 (s, 3), 4.04 (s, 3), 7.02 (s, 1), 8.24 (s, 1) ppm.

Workup

  1. temperaturethe reaction mixture was refluxed for 2 hours
  2. concentrationThe reaction mixture was concentrated under reduced pressure to a yellow solid
  3. temperatureDiphenyl ether (350 mL) was heated to 230–240° C.
  4. additionthe yellow solid was added to it
  5. temperatureThe temperature was maintained at 230–240° C. for 20 minutes
  6. additiondiluted with petroleum ether (1 L)
  7. filtrationThe solid was filtered
  8. washwashed with hot ethyl acetate

Sources & evidence

ORD record
ord-b5da2e3b23b44fc6a4a9e2f050c3a71e
Source dataset
uspto-grants-2006_02
Patent number
US06995156B2

Reaction notes

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