Ethyl Acetate → Diethyl (4-amino-3-fluorophenyl)propanedioate

HRID 889485Notes

Reaction equation

HRID 889485 reaction equation
Cl[C:2]([C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[C:15]([F:22])[CH:14]=1)([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].FC1C=C(C(C(OCC)=O)C(OCC)=O)C=CC=1[N+]([O-])=O.C(OCC)(=O)C.C([O-])=O.[NH4+]>C(O)C.[Pd]>[NH2:19][C:16]1[CH:17]=[CH:18][C:13]([CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4])=[CH:14][C:15]=1[F:22]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 2723923Ammonium formateHCID 58399560Diethyl (3-fluoro-4-nitrophenyl)propanedioateHCID 58399569Diethyl chloro(3-fluoro-4-nitrophenyl)propanedioate

Product 1

HCID 58399565Diethyl (4-amino-3-fluorophenyl)propanedioate

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

A mixture of diethyl chloro(3-fluoro-4-nitrophenyl)propanedioate and diethyl (3-fluoro-4-nitrophenyl)propanedioate (1.7 g, ˜5.7 mmol) suspended in ethanol was treated with 5-10 ml ethyl acetate until in solution. This was treated with 10% Pd/C (wet paste) (170 mg) under argon and then ammonium formate (1.8 g, 5 eq) added. Stirred for 1 hour at reflux under argon. Cooled to room temperature and Pd removed by filtration through celite, under argon. Evaporated to a brown oil ˜1.7 g. Purified by flash chromatography, 40+™M Si cartridge, eluting 5-40% ethyl acetate in hexane over 10 column volumes. Fraction evaporated to give the title compound as a yellow oil (722 mg).

Workup

  1. temperatureat reflux under argon
  2. customPd removed by filtration through celite, under argon
  3. customEvaporated to a brown oil ˜1.7 g
  4. customPurified by flash chromatography, 40+™M Si cartridge
  5. washeluting 5-40% ethyl acetate in hexane over 10 column volumes
  6. customFraction evaporated

Sources & evidence

ORD record
ord-a7a0bbf1c44744519f47b1c1d7fc5278
Source dataset
uspto-grants-2012_08
Patent number
US08252833B2

Reaction notes

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