Nitric Acid → Dimethyl 2-fluoro-5-nitrobenzene-1,4-dicarboxylate

HRID 970325

Reaction equation

HRID 970325 reaction equation
[F:1][C:2]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[N+:16]([O-])([OH:18])=[O:17]>S(=O)(=O)(O)O>[CH3:7][O:6][C:4](=[O:5])[C:3]1[CH:8]=[C:9]([N+:16]([O-:18])=[O:17])[C:10]([C:12]([O:14][CH3:15])=[O:13])=[CH:11][C:2]=1[F:1]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 79178Dimethyl 2-fluoroterephthalate

Product 1

HCID 16748390Dimethyl 2-fluoro-5-nitrobenzene-1,4-dicarboxylateYield 95%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
0 °C

Procedure

To a mixture of dimethyl 2-fluoroterephthalate (42.0 g, 0.198 mol) in concentrated sulfuric acid (200 mL) at 0° C. was added 36 mL of a 1:1 mixture of nitric acid and sulfuric acid dropwise. The mixture was stirred at 0° C. for 15 min., the ice-bath was removed, and the reaction mixture was stirred for an additional 45 min. HPLC indicated that the starting material had been consumed. The reaction mixture was poured over ice and extracted with EtOAc. The organic layer was collected, washed with brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure followed by recrystallization from MeOH afforded 48.5 g (95%) of 174A as a white solid. HPLC retention time=2.69 min. (Condition B). 1H-NMR (500 MHz, CDCl3) δ 3.95 (s, 3H), 3.98 (s, 3H), 7.44 (d, 1H), and 8.59 (d, 1H).

Workup

  1. additionwas added
  2. customthe ice-bath was removed
  3. stirringthe reaction mixture was stirred for an additional 45 min
  4. customhad been consumed
  5. additionThe reaction mixture was poured over ice
  6. extractionextracted with EtOAc
  7. customThe organic layer was collected
  8. washwashed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationConcentration under reduced pressure
  11. customfollowed by recrystallization from MeOH

Sources & evidence

ORD record
ord-ce1f9cee4e154e1297f5a4a21eed9698
Source dataset
uspto-grants-2007_12
Patent number
US07312209B2

Linked notes

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