Diethyl Oxalate → HCID 12802779, compound

HRID 1390290Notes

Reaction equation

HRID 1390290 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:20]=[CH:21][C:22]=1[Cl:23])[CH2:5][N:6]1[C:15]2[C:10](=[CH:11][C:12]([F:17])=[C:13]([F:16])[CH:14]=2)[C:9]([CH3:18])=[CH:8][C:7]1=[O:19].C(OCC)(=O)[C:25]([O:27]CC)=[O:26].[O-]CC.[K+]>C1C=CC=CC=1.C(O)C>[Cl:1][C:2]1[CH:3]=[C:4]([CH:20]=[CH:21][C:22]=1[Cl:23])[CH2:5][N:6]1[C:15]2[C:10](=[CH:11][C:12]([F:17])=[C:13]([F:16])[CH:14]=2)[C:9]([CH2:18][C:25]([OH:27])=[O:26])=[CH:8][C:7]1=[O:19]

Participants

6

Reactant 3

HCID 7268Diethyl OxalateHCID 203756291-[(3,4-Dichlorophenyl)methyl]-6,7-difluoro-4-methylquinolin-2(1H)-oneHCID 23670592Potassium ethoxide

Product 1

HCID 12802779HCID 12802779, compoundYield 10%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 1-(3,4-dichlorobenzyl)-6,7-difluoro-1,2-dihydro-4-methyl-2-oxoquinoline (5 g.) in benzene (15 ml.) was added with stirring at ambient temperature to a mixture of diethyl oxalate (2.3 g.), benzene (2 ml.) and a 6N-solution of potassium ethoxide in ethanol (6 ml.). The mixture was allowed to stand overnight at ambient temperature under dry nitrogen. The yellow solid was filtered off, washed with benzene (5 ml.) and dried by suction on the filter. The dried solid (5.7 g.) was mixed with 2.77 N-aqueous sodium hydroxide (21 ml.) at 0° C. and kept at 0° C. overnight. Ice (11.5 g.) and then 100 vol. hydrogen peroxide (4.04 ml.) were added to the mixture and it was again kept overnight at 0° C. A further quantity of 100 vol. hydrogen peroxide (1.7 ml.) was added and the mixture kept at 0° C. for 72 hours. The mixture was then treated with manganese dioxide (1 g.). When the effervescence had ceased the mixture was warmed to 50° C. and filtered. The filter cake was washed with warm 2.77 N-aqueous sodium hydroxide (20 ml.) and the total filtrate acidified with concentrated hydrochloric acid. The precipitate was collected and recrystallised first from a mixture (1/2 v/v) of ethyl acetate and cyclohexane, and then from ethanol to give 1-(3,4-dichlorobenzyl)-6,7-difluoro-1,2-dihydro-2-oxoquinol-4-yl-acetic acid m.p. 185°-7° C. (dec.), in 10% yield.

Workup

  1. filtrationThe yellow solid was filtered off
  2. washwashed with benzene (5 ml.)
  3. customdried by suction on the filter
  4. additionThe dried solid (5.7 g.) was mixed with 2.77 N-aqueous sodium hydroxide (21 ml.) at 0° C.
  5. waitkept at 0° C. overnight
  6. additionIce (11.5 g.) and then 100 vol. hydrogen peroxide (4.04 ml.) were added to the mixture and it
  7. waitwas again kept overnight at 0° C
  8. additionA further quantity of 100 vol. hydrogen peroxide (1.7 ml.) was added
  9. waitthe mixture kept at 0° C. for 72 hours
  10. additionThe mixture was then treated with manganese dioxide (1 g.)
  11. filtrationfiltered
  12. washThe filter cake was washed
  13. temperaturewith warm 2.77 N-aqueous sodium hydroxide (20 ml.)
  14. customThe precipitate was collected
  15. customrecrystallised first from a mixture (1/2 v/v) of ethyl acetate and cyclohexane

Sources & evidence

ORD record
ord-7b465a4b87e5493abe022096439e9966
Source dataset
uspto-grants-1979_02
Patent number
US04138490

Reaction notes

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