Ethyl 4,4,4-trifluoroacetoacetate → 5-amino-7-chloro-3,4-dihydro-4-hydroxy-4-(trifluoromethyl)-1H-quinolin-2-one

HRID 1350131Notes

Reaction equation

HRID 1350131 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH2:9])[CH:5]=[C:6]([NH2:8])[CH:7]=1.[F:10][C:11]([F:21])([F:20])[C:12](=[O:19])[CH2:13][C:14](OCC)=[O:15]>C(O)C>[NH2:8][C:6]1[CH:7]=[C:2]([Cl:1])[CH:3]=[C:4]2[C:5]=1[C:12]([OH:19])([C:11]([F:21])([F:20])[F:10])[CH2:13][C:14](=[O:15])[NH:9]2

Participants

4

Reactant 2

HCID 67793Ethyl 4,4,4-trifluoroacetoacetateHCID 733351,3-Benzenediamine, 5-chloro-

Product 1

HCID 222791795-amino-7-chloro-3,4-dihydro-4-hydroxy-4-(trifluoromethyl)-1H-quinolin-2-oneYield 37%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 5-chloro-1,3-phenylenediamine (15.0 g, 0.105 mol) in 70 mL ethanol was added ethyl 4,4,4-trifluoroacetoacetate (20.4 g, 0.111 mol), then the mixture was heated at reflux for 18 h. The solvent was removed under reduced pressure until the product began to precipitate. The material was allowed to crystallize for 2 h, whereupon it was filtered and rinsed with cold ether to afford 10.9 g (37%) of 5-amino-7-chloro-3,4-dihydro-4-hydroxy-4-(trifluoromethyl)-1H-quinolin-2-one, a tan solid. The filtrate was concentrated until solid began to precipitate and afforded an additional 3.0 g (10%). 1H NMR (400 MHz, acetone-d6) δ 11.0 (broad s, 1H), 9.64 (s, 1H), 7.42 (t, 1H, J=8.1), 6.99 (d, 1H, J=8.1), 6.90 (s, 1H), 6.79 (d, 1H, J=8.1).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 18 h
  3. customThe solvent was removed under reduced pressure until the product
  4. customto precipitate
  5. customto crystallize for 2 h, whereupon it
  6. filtrationwas filtered
  7. washrinsed with cold ether

Sources & evidence

ORD record
ord-34d282bd727d45d7bb7205cb97055b8a
Source dataset
uspto-grants-2007_05
Patent number
US07214690B2

Reaction notes

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