Dichloromethane → ethyl 6,7-dimethoxy-2-methyl-4-oxo-3,4-dihydro-1(2H)-quinolinecarboxylate

HRID 597194Notes

Reaction equation

HRID 597194 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[NH:9][CH:8]([CH3:15])[CH2:7][C:6]2=[O:16].C(=O)([O-])[O-].[K+].[K+].C(Cl)Cl.Cl[C:27]([O:29][CH2:30][CH3:31])=[O:28]>CCCCCC.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[N:9]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH:8]([CH3:15])[CH2:7][C:6]2=[O:16]

Participants

7

Reactant 4

HCID 6344Dichloromethane2×HCID 10928Ethyl chloroformate2×HCID 11430Potassium Carbonate2×HCID 214397206,7-Dimethoxy-2-methyl-2,3-dihydroquinolin-4(1H)-one

Product 1

HCID 15480676ethyl 6,7-dimethoxy-2-methyl-4-oxo-3,4-dihydro-1(2H)-quinolinecarboxylate

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 15 g. of the quinoline product of Example 4, 95 g. of potassium carbonate, and 225 ml. of methylene chloride was stirred for 1 hr., then 14.7 g. of ethyl chloroformate in 20 ml. of methylene chloride was added dropwise and the suspension was allowed to stir for 72 hrs. at room temperature. Additional 7.3 g. portions of ethyl chloroformate were added after 24 and 48 hrs. and 47 g. of potassium carbonate was added after 48 hrs. The reaction mixture was quenched with water and extracted several times with methylene chloride. The combined organic extracts were washed with water, dried over magnesium sulfate and concentrated under reduced pressure to give an oil which solidified upon standing; trituration with 5% ethyl acetate in hexane gave 17 g. of a solid, m.p. 112°-116°. This solid was chromatographed on silica gel, eluting with 1:1 ethyl acetate/hexane, and recrystallized from 1:1 ethyl acetate/hexane to give 13.9 g. of white crystals, m.p. 116.5°-18°.

Workup

  1. additionA mixture of 15 g
  2. customat room temperature
  3. customThe reaction mixture was quenched with water
  4. extractionextracted several times with methylene chloride
  5. washThe combined organic extracts were washed with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customto give an oil which
  9. customThis solid was chromatographed on silica gel
  10. washeluting with 1:1 ethyl acetate/hexane
  11. customrecrystallized from 1:1 ethyl acetate/hexane
  12. customto give 13.9 g

Sources & evidence

ORD record
ord-24005724eca54afa811cec7250bfa994
Source dataset
uspto-grants-1977_03
Patent number
US04013662

Reaction notes

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