Urea → HCID 67271258, compound

HRID 600907

Reaction equation

HRID 600907 reaction equation
N[C:2]1[CH:11]=[C:10]([F:12])[C:9]([CH3:13])=[C:8]2[C:3]=1[C:4](=[O:23])[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:6][N:7]2[C@@H:14]1[CH2:16][C@@H:15]1[F:17].N([O-])=[O:25].[Na+].NC(N)=O.C(Cl)(Cl)Cl>S(=O)(=O)(O)O.O.O.O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[Cu-]=O>[F:12][C:10]1[C:9]([CH3:13])=[C:8]2[C:3]([C:4](=[O:23])[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:6][N:7]2[C@@H:14]2[CH2:16][C@@H:15]2[F:17])=[C:2]([OH:25])[CH:11]=1

Participants

8

Reactant 4

HCID 1176UreaHCID 6212ChloroformHCID 23668193Sodium NitriteHCID 67270424HCID 67270424, compound

Product 1

HCID 67271258HCID 67271258, compoundYield 21%

Reagents, catalysts & solvents 3

HCID 9837674Copper(II) nitrate trihydrateCatalystHCID 178419072HCID 178419072, compoundCatalystHCID 1118Sulfuric AcidSolvent

Conditions

Temperature
0 °C

Procedure

Ethyl 5-amino-7-fluoro-1-[2-(S)-fluoro-1-(R)-cyclopropyl]-8-methyl-1,4-dihydro-4-oxoquinoline-3-carboxylate (1.414 g, 4.39 mmol) was suspended in 35% aqueous sulfuric acid solution (15 ml), and while cooling with ice, an aqueous sodium nitrite solution (394 mg, 5.70 mmol/4.5 ml) was dripped therein over a period of 5 minutes. After then stirring at 0° C. for 30 minutes, a small amount of urea was added, and at the same temperature, an aqueous copper (II) nitrate trihydrate solution (17.00, 70.2 mmol/155 ml) was dripped therein over a period of 10 minutes. After stirring at 0° C. for 5 minutes, copper (I) oxide (565 mg, 3.95 mmol) was added while stirring the reaction solution violently. After then stirring at room temperature for 20 minutes, extraction into chloroform (200 ml×2) was performed, and after making the aqueous layer slightly basic with sodium bicarbonate, the aqueous layer was extracted with chloroform (150 ml×3). The combined organic layer was then dried over anhydrous sodium sulfate, and after removing the drying agent bt the filtration, the solvent was evaporated under a reduced pressure. The crude product obtained was then subject to a silica gel chromatography, thereby obtaining 297 mg (21%) of the title compound as a yellow powder from a chloroform:methanol=10:1 eluate.

Workup

  1. temperaturewhile cooling with ice
  2. waitover a period of 10 minutes
  3. stirringAfter stirring at 0° C. for 5 minutes
  4. stirringwhile stirring the reaction solution violently
  5. stirringAfter then stirring at room temperature for 20 minutes
  6. extractionextraction into chloroform (200 ml×2)
  7. extractionthe aqueous layer was extracted with chloroform (150 ml×3)
  8. dry with materialThe combined organic layer was then dried over anhydrous sodium sulfate
  9. customafter removing the drying agent
  10. filtrationbt the filtration
  11. customthe solvent was evaporated under a reduced pressure
  12. customThe crude product obtained

Sources & evidence

ORD record
ord-7378c4ad5c064a6794b226243def28f3
Source dataset
uspto-grants-2011_03
Patent number
US07902226B2

Linked notes

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