Diethyl (ethoxymethylene)malonate → Diethyl 2-((4-fluoro-3-nitroanilino)methylene)malonate
Reaction equation
[F:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH2:12]([O:14][C:15](=[O:26])[C:16](=[CH:22]OCC)[C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH3:13]>CCCCCC>[CH2:12]([O:14][C:15](=[O:26])[C:16](=[CH:22][NH:6][C:5]1[CH:7]=[CH:8][C:2]([F:1])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1)[C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH3:13]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Procedure
50 g of 4-fluoro-3-nitroaniline and 69 g of ethoxymethylene malonic acid-diethyl ester were heated for 3 hours to 120° C. The mixture was added to n-hexane, stirred for 2 hours, and the crystalline material was suctioned off and dried in a vacuum at room temperature. 93 g of N-(4-fluoro-3-nitrophenyl)-aminomethylene malonic acid diethyl ester is obtained. The latter is added in 3 portions of 31 g to respectively 150 ml of a mixture that consists of 26.5% diphenyl and 73.5% diphenyl ether (DOWTHERM A⊕) that is preheated to 260° C., and it is stirred for 30 minutes at this temperature. After cooling, it is diluted with 500 ml of n-hexane, and the precipitate is suctioned off. A total of 64 g of a mixture of 1,4-dihydro-6-fluoro-5-nitro-4-oxo-quinoline-3-carboxylic acid ethyl ester and 1,4-dihydro-6-fluoro-7-nitro-4-oxo-quinoline-3-carboxylic acid-ethyl ester is obtained.
Workup
- customdried in a vacuum at room temperature
Sources & evidence
- ORD record
- ord-63752be6824d418ab9f52dc275fb6b83
- Source dataset
- uspto-grants-2004_09
- Patent number
- US06790858B2
Reaction notes
Loading…