p-Fluoronitrobenzene → HCID 54428535, compound

HRID 481974Notes

Reaction equation

HRID 481974 reaction equation
[H-].[K+].[CH3:3][N:4]([CH3:12])[CH2:5][CH2:6][CH2:7][C:8](=[N:10][OH:11])[CH3:9].[N+:13]([C:16]1[CH:21]=[CH:20][C:19](F)=[CH:18][CH:17]=1)([O-:15])=[O:14].C1OCCOCCOCCOCCOCCOC1.C(=O)([O-])[O-].[K+].[K+]>O1CCCC1>[N+:13]([C:16]1[CH:21]=[CH:20][C:19]([O:11][N:10]=[C:8]([CH2:7][CH2:6][CH2:5][N:4]([CH3:12])[CH3:3])[CH3:9])=[CH:18][CH:17]=1)([O-:15])=[O:14]

Participants

7

Reactant 5

HCID 9590p-FluoronitrobenzeneHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 82127Potassium hydrideHCID 73516726HCID 73516726, compound

Product 1

HCID 54428535HCID 54428535, compoundYield 40.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A suspension of 15.0 gm (82 mMol) potassium hydride (22% dispersion in mineral oil) in 10 mL tetrahydrofuran was cooled in an ice bath. To this suspension was slowly added a solution of 9.8 gm (68 mMol) N,N-dimethyl-5-amino-2-pentanone oxime in 20 mL tetrahydrofuran resulting in vigorous gas evolution. Once this addition was complete, a solution of 12.5 gm (88.3 mMol) 4-nitrofluorobenzene and 0.90 gm (3.4 mMol) 18-crown-6 in 10 mL tetrahydrofuran were added. The dark solution was stirred for 1 hour at ice bath temperature and then for 3 hours at room temperature. The reaction mixture was then poured into 100 mL of aqueous 5% potassium carbonate and the resulting mixture was extracted with dichloromethane. These organic extracts were combined, washed with aqueous 5% potassium carbonate, dried over sodium sulfate and concentrated under reduced pressure. The residual oil was subjected to flash silica gel chromatography, eluting with 10% methanol in dichloromethane. Fractions containing product were combined and concentrated under reduced pressure to provide 7.3 gm (40%) of the desired oxime ether as a dark oil.

Workup

  1. temperaturewas cooled in an ice bath
  2. additionOnce this addition
  3. waitfor 3 hours at room temperature
  4. extractionthe resulting mixture was extracted with dichloromethane
  5. washwashed with aqueous 5% potassium carbonate
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. washeluting with 10% methanol in dichloromethane
  9. additionFractions containing product
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-36f76cbdbd074bcc849f4b774c5def86
Source dataset
uspto-grants-1998_08
Patent number
US05792763

Reaction notes

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