Hydrochloric Acid → 1-(2-Chloro-4-fluoro-5-methylcarbonylaminophenyl)ethyl nitrate

HRID 231415Notes

Reaction equation

HRID 231415 reaction equation
[N+:1]([O-:17])([O:3][CH:4]([C:6]1[CH:11]=[C:10]([N+:12]([O-])=O)[C:9]([F:15])=[CH:8][C:7]=1[Cl:16])[CH3:5])=[O:2].[C:18](OC(=O)C)(=[O:20])[CH3:19].[H][H].Cl>[Pt]=O.O.C(OCC)(=O)C>[N+:1]([O-:17])([O:3][CH:4]([C:6]1[CH:11]=[C:10]([NH:12][C:18]([CH3:19])=[O:20])[C:9]([F:15])=[CH:8][C:7]=1[Cl:16])[CH3:5])=[O:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7918Acetic AnhydrideHCID 14501806HCID 14501806, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 145018071-(2-Chloro-4-fluoro-5-methylcarbonylaminophenyl)ethyl nitrate

Reagents, catalysts & solvents 3

HCID 82844Platinum oxide (PtO)CatalystHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

In a Parr hydrogenation apparatus were placed 3.7 g (0.014 mole) of 1-(2-chloro-4-fluoro-5-nitrophenyl)ethyl nitrate, 0.35 g of platinum oxide catalyst, 35 ml of ethyl acetate, and 10 ml of acetic anhydride. The apparatus was pressurized with hydrogen, and the reaction was allowed to continue until the pressure ceased dropping. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure leaving a residue. This residue was mixed with 15 ml of water and 5 ml of 10% hydrochloric acid. This mixture was stirred at room temperature for two hours. Following dilution with water, the mixture was extracted with methylene chloride. The extracts were combined and washed successively with water, 5% hydrochloric acid, and a saturated, aqueous solution of sodium bicarbonate. This solution was dried, filtered, and the solvent was evaporated under reduced pressure leaving a residue. This residue was passed through a column of silica gel, eluting first with ethyl acetate/heptane (1/4) and then with ethyl acetate/heptane (1/1). The appropriate fractions were collected, and the solvent was evaporated under reduced pressure yielding 1.7 g of 1-(2-chloro-4-fluoro-5-methylcarbonylaminophenyl)ethyl nitrate as a white solid. The nmr and ir spectra were consistent with the proposed structure.

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. customleaving a residue
  4. extractionthe mixture was extracted with methylene chloride
  5. washwashed successively with water, 5% hydrochloric acid
  6. customThis solution was dried
  7. filtrationfiltered
  8. customthe solvent was evaporated under reduced pressure
  9. customleaving a residue
  10. washeluting first with ethyl acetate/heptane (1/4)
  11. customThe appropriate fractions were collected
  12. customthe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-e963942e100b41f8b8c668601e82eeea
Source dataset
uspto-grants-1989_07
Patent number
US04846875

Reaction notes

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