Ethanol → Ethyl 1-ethyl-5,6-dihydroxy-4-oxo-1,4-dihydroquinoline-3-carboxylate

HRID 525959Notes

Reaction equation

HRID 525959 reaction equation
[CH2:1]([N:3]1[C:12]2[C:7](=[C:8]([O:15]C)[C:9]([O:13]C)=[CH:10][CH:11]=2)[C:6](=[O:17])[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:4]1)[CH3:2].B(Br)(Br)Br.CCO>ClCCl>[CH2:1]([N:3]1[C:12]2[C:7](=[C:8]([OH:15])[C:9]([OH:13])=[CH:10][CH:11]=2)[C:6](=[O:17])[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:4]1)[CH3:2]

Participants

5

Reactant 3

HCID 702EthanolHCID 25134Boron tribromideHCID 86732824Ethyl 1-ethyl-5,6-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate

Product 1

HCID 86732826Ethyl 1-ethyl-5,6-dihydroxy-4-oxo-1,4-dihydroquinoline-3-carboxylateYield 45.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a brown solution of ethyl 1-ethyl-5,6-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate (6 g, 19.65 mmol) in Dichloromethane (DCM) (100 mL) was added BBr3 (6.13 mL, 64.8 mmol) dropwise and the mixture was stirred at r.t. overnight. The resulting mixture was carefully poured into EtOH (50 mL) at −40° C. and the mixture was stirred at r.t. over the weekend. The precipitates were collected by filtration and washed with DCM and MeOH. The filtrate was concentrated a bit, the precipitates were collected and washed by DCM. The solids were combined to afford ethyl 1-ethyl-5,6-dihydroxy-4-oxo-1,4-dihydroquinoline-3-carboxylate (5 g, 9.02 mmol, 45.9% yield) as a yellow solid that contained also some 1-ethyl-5,6-dihydroxy-4-oxo-1,4-dihydroquinoline-3-carboxylic acid. This mixture was directly used in the next step without further purification. LCMS: (M+H)+: 278.4 (ester); 250.3 (acid).

Workup

  1. stirringthe mixture was stirred at r.t. over the weekend
  2. filtrationThe precipitates were collected by filtration
  3. washwashed with DCM and MeOH
  4. concentrationThe filtrate was concentrated a bit
  5. customthe precipitates were collected
  6. washwashed by DCM

Sources & evidence

ORD record
ord-841f185ff9694f29baf032a76614cba7
Source dataset
uspto-grants-2016_05
Patent number
US09340556B2

Reaction notes

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