HCID 57995528, compound → HCID 57995587, compound

HRID 1183629Notes

Reaction equation

HRID 1183629 reaction equation
[CH2:1]([O:3][C:4](=[O:32])[CH:5]([C:11]1[CH:16]=[C:15]([O:17][CH2:18][C:19]([F:22])([F:21])[F:20])[C:14]([N+:23]([O-:25])=[O:24])=[C:13]([O:26][CH2:27][C:28]([F:31])([F:30])[F:29])[CH:12]=1)C(OCC)=O)[CH3:2]>CC(O)=O>[CH2:1]([O:3][C:4](=[O:32])[CH2:5][C:11]1[CH:12]=[C:13]([O:26][CH2:27][C:28]([F:31])([F:30])[F:29])[C:14]([N+:23]([O-:25])=[O:24])=[C:15]([O:17][CH2:18][C:19]([F:21])([F:22])[F:20])[CH:16]=1)[CH3:2]

Participants

3

Reactant 1

HCID 57995528HCID 57995528, compound

Product 1

HCID 57995587HCID 57995587, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Crude 2-[4-nitro-3,5-bis-(2,2,2-trifluoro-ethoxy)-phenyl]-malonic acid diethyl ester (20.8 g, 43.6 mmol) was dissolved in a mixture of AcOH/12 N HCl (150 mL/150 mL) and the reaction mixture was refluxed for 16 h. The solvent was evaporated and water (100 mL) was added. The reaction mixture was extracted with EtOAc (3×100 mL). The organic layers were combined, washed with water (3×100 mL), and dried over MgSO4. The solvent was evaporated under reduced pressure to give a brown solid, which was washed with a mixture of Heptane/Et2O (100 mL/100 mL) to give [4-nitro-3,5-bis-(2,2,2-trifluoro-ethoxy)-phenyl]-acetic acid ethyl ester as a solid (10.0 g, 57%). 1H NMR (300 MHz, CDCl3/TMS): δ 6.71 (s, 2H), 4.45 (q, J=7.7 Hz, 4H), 4.18 (q, J=7.2 Hz, 2H), 3.63 (s, 2H), 1.28 (t, J=7.1 Hz, 6H). 13C NMR (75 MHz, CDCl3/TMS): δ 169.7, 149.6, 138.5, 132.4, 122.4 (q, 1JCF=277.6 Hz), 109.4 (two signals), 67.0 (q, 2JCF=37.2 Hz), 61.6, 41.4, 14.2.

Workup

  1. temperaturethe reaction mixture was refluxed for 16 h
  2. customThe solvent was evaporated
  3. additionwater (100 mL) was added
  4. extractionThe reaction mixture was extracted with EtOAc (3×100 mL)
  5. washwashed with water (3×100 mL)
  6. dry with materialdried over MgSO4
  7. customThe solvent was evaporated under reduced pressure
  8. customto give a brown solid, which
  9. washwas washed with a mixture of Heptane/Et2O (100 mL/100 mL)

Sources & evidence

ORD record
ord-7025c94b3a8f468fa3d43449d97ac197
Source dataset
uspto-grants-2014_03
Patent number
US08664249B2

Reaction notes

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