Diethyl (ethoxymethylene)malonate → HCID 13577655, compound

HRID 2418240Notes

Reaction equation

HRID 2418240 reaction equation
FC1C(OC)=C2C(=CC=1)NC(C)CC2.C(OC=C(C(OCC)=O)C(OCC)=O)C.[F:30][C:31]1[CH:43]=[C:41]2[C:42]3[N:37]([CH:38]=[C:39]([C:45]([O:47]CC)=[O:46])[C:40]2=[O:44])[CH:36]([CH3:50])[CH2:35][CH2:34][C:33]=3[C:32]=1[O:51][CH3:52]>O.[OH-].[Na+]>[F:30][C:31]1[CH:43]=[C:41]2[C:42]3[N:37]([CH:38]=[C:39]([C:45]([OH:47])=[O:46])[C:40]2=[O:44])[CH:36]([CH3:50])[CH2:35][CH2:34][C:33]=3[C:32]=1[O:51][CH3:52]

Participants

6

Reactant 3

HCID 6871Diethyl (ethoxymethylene)malonateHCID 13577654HCID 13577654, compoundHCID 20248485HCID 20248485, compound

Product 1

HCID 13577655HCID 13577655, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
140 °C

Procedure

A mixture of 1.2 g of 6-fluoro-5-methoxy-1,2,3,4-tetrahydroquinaldine and 2.5 g of diethyl ethoxymethylenemalonate was heated at 140° C. for 3 hours, and was then cooled to 100° C. To the crude hot diethyl 2-[N-(6-fluoro-5-methoxy-1,2,3,4-tetrahydroquinaldinyl)]methylenemalonate was added 25 g of polyphosphoric acid, and the mixture was heated on a steam bath for one hour. The mixture containing ethyl 6,7-dihydro-9-fluoro-8-methoxy-5-methyl-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylate was cooled to about 20° C., diluted with an equal volume of water and basified with 50% sodium hydroxide solution. This solution was heated at its reflux temperature for two hours and filtered hot through celite. The filtrate was cooled to about 20° C. and acidified with concentrated hydrochloric acid. The solid was separated by filtration to provide 1.2 g of off-white 6,7-dihydro-9-fluoro-8-methoxy-5-methyl-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acid. Recrystallization from aqueous N,N-dimethylformamide provided pure product, m.p. 234°-236° C. Analysis: Calculated for C15H14FNO4 : %C, 61.8; %H, 4.8; %N, 4.8; Found: %C, 61.7; %H, 4.6; %N, 4.8.

Workup

  1. temperaturewas then cooled to 100° C
  2. temperaturethe mixture was heated on a steam bath for one hour
  3. temperaturewas cooled to about 20° C.
  4. temperatureThis solution was heated at its
  5. temperaturereflux temperature for two hours
  6. filtrationfiltered hot through celite
  7. temperatureThe filtrate was cooled to about 20° C.
  8. customThe solid was separated by filtration

Sources & evidence

ORD record
ord-da88de391790417eb5ea4c1e964fa122
Source dataset
uspto-grants-1984_09
Patent number
US04472407

Reaction notes

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