Dimethyl 2-fluoro-5-nitrobenzene-1,4-dicarboxylate → Dimethyl 2-amino-5-fluoroterephthalate

HRID 970326Notes

Reaction equation

HRID 970326 reaction equation
[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:13]=[C:12]([N+:14]([O-])=O)[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[F:17]>CCOC(C)=O.[Pd]>[CH3:11][O:10][C:8](=[O:9])[C:7]1[CH:6]=[C:5]([F:17])[C:4]([C:3]([O:2][CH3:1])=[O:18])=[CH:13][C:12]=1[NH2:14]

Participants

4

Reactant 1

HCID 16748390Dimethyl 2-fluoro-5-nitrobenzene-1,4-dicarboxylate

Product 1

HCID 16748146Dimethyl 2-amino-5-fluoroterephthalateYield 90%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 174A (48.5 g, 0.178 mol) and palladium/carbon (4.6 g) in EtOAc (450 mL) was evacuated under reduced pressure and charged with hydrogen (3×). The reaction mixture was subsequently stirred under a steady stream of nitrogen for 1 h. The reaction mixture was filtered through a pad of Celite, concentrated, and recrystallized form a mixture of MeOH and DCM to provide 36.2 g (90%) of 174B as a bright yellow solid. HPLC retention time=2.68 min. (Condition B), and LC/MS M+1=228. 1H-NMR (500 MHz, CDCl3) δ 3.89 (s, 3H), 3.92 (s, 3H), 7.20 (d, 1H), and 7.61 (d, 1H).

Workup

  1. customwas evacuated under reduced pressure
  2. additioncharged with hydrogen (3×)
  3. filtrationThe reaction mixture was filtered through a pad of Celite
  4. concentrationconcentrated
  5. customrecrystallized form
  6. additiona mixture of MeOH and DCM

Sources & evidence

ORD record
ord-9570c85cd3ca445a9497dd2248294264
Source dataset
uspto-grants-2007_12
Patent number
US07312209B2

Reaction notes

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