Ethanol → HCID 57917364, compound

HRID 1942057Notes

Reaction equation

HRID 1942057 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([F:11])[CH:3]=1.O[CH2:13][CH:14]([CH2:16]O)O.[CH3:18][CH2:19][OH:20].[OH-].[NH4+]>S(=O)(=O)(O)O>[CH2:18]([O:7][C:6]([C:5]1[C:4]([F:11])=[C:3]2[C:2](=[CH:10][CH:9]=1)[N:1]=[CH:16][CH:14]=[CH:13]2)=[O:8])[CH3:19].[CH2:19]([O:20][C:6]([C:5]1[CH:9]=[C:10]2[C:2](=[CH:3][C:4]=1[F:11])[N:1]=[CH:16][CH:14]=[CH:13]2)=[O:8])[CH3:18]

Participants

7

Reactant 4

HCID 702EthanolHCID 753GlycerolHCID 14923Ammonium HydroxideHCID 3026804-Amino-2-fluorobenzoic acid

Product 2

HCID 57917364HCID 57917364, compoundHCID 57917442Ethyl 5-fluoro-6-quinolinecarboxylate

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
100 °C

Procedure

To a suspension of 4-amino-2-fluoro-benzoic acid (1 g, 6.38 mmol) in sulfuric acid 75% (15 mL) were added glycerol anhydrous (2.108 mL, 28.72 mmol) and sodium 3-nitrosulfonate (2.93 g, 12.8 mmol). The mixture was stirred at 100° C. for 4 h. It was then cooled down to 60° C. and EtOH was added. The mixture was then stirred at 60° C. for 45 h. The solution was poured into ice-water mixture and then basified with saturated aqueous ammonium hydroxide. It was extracted twice with EtOAc. The organic phases were joined and washed with brine, dried over Na2SO4 and concentrated. The residue was purified by MPLC eluting with a DCM/MeOH gradient to afford a yellow oil as a mixture (1:1) of 5-fluoro-quinoline-6-carboxylic acid ethyl ester and 7-fluoro-quinoline-6-carboxylic acid ethyl ester (tR 1.3 min and tR 1.1 min (conditions 6), MH+=220).

Workup

  1. temperatureIt was then cooled down to 60° C.
  2. stirringThe mixture was then stirred at 60° C. for 45 h
  3. extractionIt was extracted twice with EtOAc
  4. washwashed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was purified by MPLC
  8. washeluting with a DCM/MeOH gradient

Sources & evidence

ORD record
ord-f0b0b54082d04dc49ccfbc5bd890a6cb
Source dataset
uspto-grants-2013_03
Patent number
US08389526B2

Reaction notes

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