Diethyl (ethoxymethylene)malonate → 7-Chloro-1-ethyl-1,4-dihydro-8-methyl-4-oxo-3-quinolinecarboxylic acid

HRID 463798Notes

Reaction equation

HRID 463798 reaction equation
[CH2:1]([NH:3][C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([Cl:10])[C:5]=1[CH3:11])[CH3:2].C([O:14][CH:15]=[C:16]([C:22](OCC)=O)[C:17]([O:19]CC)=[O:18])C>O>[CH2:1]([N:3]1[C:4]2[C:9](=[CH:8][CH:7]=[C:6]([Cl:10])[C:5]=2[CH3:11])[C:15](=[O:14])[C:16]([C:17]([OH:19])=[O:18])=[CH:22]1)[CH3:2]

Participants

4

Reactant 2

HCID 6871Diethyl (ethoxymethylene)malonateHCID 13491698HCID 13491698, compound

Product 1

HCID 134916997-Chloro-1-ethyl-1,4-dihydro-8-methyl-4-oxo-3-quinolinecarboxylic acidYield 70.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
110 °C

Procedure

Ten grams of N-ethyl-2-methyl-3-chloroaniline is allowed to react with 15 g of diethyl ethoxymethylenemalonate under heating at 110° C. for 30 minutes. Then, polyphosphoric acid (obtained from 50 g each of phosphoric acid and phosphorus pentaoxide) is added to be subjected to the reaction at 140° C. for 40 minutes. After the reaction, the mixture is poured into 600 g of water and ice, resulting in crystals separated out. The crystals are recovered by filtration, and a 10% sodium hydroxide solution is added to the fitrate and the mixture is refluxed for 1 hour. After refluxing, the mixture is treated with activated carbon and adjusted to pH 2 with concentrated hydrochloric acid, whereby there separate out light yellow crystals. Recrystallization from dimethylformamide yields 11 g of 1-ethyl-7-chloro-8-methyl-4-oxo-1,4-dihydroquinoline-3-carboxylic acid as the white, needle-like crystals. mp. 221°-222° C.

Workup

  1. customto be subjected to the reaction at 140° C. for 40 minutes
  2. customAfter the reaction
  3. customresulting in crystals
  4. customseparated out
  5. filtrationThe crystals are recovered by filtration
  6. additiona 10% sodium hydroxide solution is added to the fitrate
  7. temperaturethe mixture is refluxed for 1 hour
  8. temperatureAfter refluxing
  9. additionthe mixture is treated with activated carbon
  10. customseparate out light yellow crystals
  11. customRecrystallization from dimethylformamide

Sources & evidence

ORD record
ord-45b8fc979c5e4c47ab78b61d019fe211
Source dataset
uspto-grants-1985_10
Patent number
US04544747

Reaction notes

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