Diethyl (ethoxymethylene)malonate → HCID 21408193, compound

HRID 1283805Notes

Reaction equation

HRID 1283805 reaction equation
[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][CH:7]([CH3:12])[CH2:6][C:5]2=[O:13].C([O:16][CH:17]=[C:18]([C:24](OCC)=O)[C:19]([O:21][CH2:22][CH3:23])=[O:20])C>>[O:16]=[C:17]1[C:10]2=[CH:11][C:2]([F:1])=[CH:3][C:4]3=[C:9]2[N:8]([CH:7]([CH3:12])[CH2:6][C:5]3=[O:13])[CH:24]=[C:18]1[C:19]([O:21][CH2:22][CH3:23])=[O:20]

Participants

3

Reactant 2

HCID 6871Diethyl (ethoxymethylene)malonateHCID 214081896-Fluoro-2-methyl-2,3-dihydroquinolin-4(1H)-one

Product 1

HCID 21408193HCID 21408193, compound

Conditions

Temperature
170 °C

Procedure

A stirred mixture of 12 g (0.067 mole) of 6-fluoro-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline from example 4 and 14.8 g (0.070 mole) of diethyl ethoxymethylenemalonate was heated gradually to 160 to 180° C. while removing the ethanol generated by distillation. After 0.5 hour the mixture was cooled to 60°C., and 30 g of polyphosphoric acid was added. This mixture was heated gradually to 150 to 160°C. and maintained at 155° to 160°C. for 5 to 10 minutes. Following cooling, water was added, and the mixture was kneaded to produce an orange powder which was separated by filtration. Recrystallization from a mixture of 500 ml of 95% ethanol and 100 ml of glacial acetic acid gave a yellow product, ethyl 6,7-dihydro-1,7-dioxo-9-fluoro-5-methyl-1H,5H-benzo[ij]-quinolizine2-carboxylate, m.p. 262-265°C.

Workup

  1. customwhile removing the ethanol
  2. distillationgenerated by distillation
  3. temperatureAfter 0.5 hour the mixture was cooled to 60°C.
  4. addition30 g of polyphosphoric acid was added
  5. temperatureThis mixture was heated gradually to 150 to 160°C.
  6. temperaturemaintained at 155° to 160°C. for 5 to 10 minutes
  7. temperatureFollowing cooling
  8. additionwater was added
  9. customto produce an orange powder which
  10. customwas separated by filtration
  11. customRecrystallization
  12. additionfrom a mixture of 500 ml of 95% ethanol and 100 ml of glacial acetic acid

Sources & evidence

ORD record
ord-95d182286b354cdbab9610e5df0691dc
Source dataset
uspto-grants-1976_08
Patent number
US03976651

Reaction notes

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