Acetic Acid → Tert-butyl 2-cyano-2-(3-methoxy-4-nitrophenyl)acetate

HRID 1262315Notes

Reaction equation

HRID 1262315 reaction equation
F[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([O:11][CH3:12])[CH:3]=1.CC(C)([O-])C.[K+].O1CCCC1.[C:24]([CH2:26][C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])#[N:25].C(O)(=O)C>>[C:30]([O:29][C:27](=[O:28])[CH:26]([C:24]#[N:25])[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([O:11][CH3:12])[CH:3]=1)([CH3:33])([CH3:32])[CH3:31]

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 8028TetrahydrofuranHCID 70693tert-Butyl cyanoacetateHCID 27792505-Fluoro-2-nitroanisoleHCID 23665647Potassium tert-butoxide

Product 1

HCID 66712431Tert-butyl 2-cyano-2-(3-methoxy-4-nitrophenyl)acetateYield 50%

Conditions

Temperature
80 °C

Procedure

Into a seal vessel, 4-Fluoro-2-methoxy-1-nitro-benzene (15.00 g, 87.65 mmol), 1.00 M of Potassium tert-Butoxide in Tetrahydrofuran (193 mL, 193 mmol), and t-Butyl cyanoacetate (24.7 g, 175 mmol) were added. The reaction mixture was heated at 80° C. for 4 hours. The reaction was cooled to room temperature. Acetic acid (10.96 mL, 192.8 mmol) was added. The reaction was partitioned with water and DCM. The organic was separated, washed with Brine and dried over Na2SO4. The solid was filtered and washed with DCM. The solvent was removed under vacuum. The reaction mixture was purified via ISCO column chromatography with hexane and EtOAc. The reaction mixture was purified via ISCO column chromatography with hexane and EtOAc. The collected fractions afforded an orange collected fractions afforded Cyano-(3-methoxy-4-nitro-phenyl)-acetic acid tert-butyl ester as an orange solid (12.8 g, 49%).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. customThe reaction was partitioned with water and DCM
  3. customThe organic was separated
  4. washwashed with Brine
  5. dry with materialdried over Na2SO4
  6. filtrationThe solid was filtered
  7. washwashed with DCM
  8. customThe solvent was removed under vacuum
  9. customThe reaction mixture was purified via ISCO column chromatography with hexane and EtOAc
  10. customThe reaction mixture was purified via ISCO column chromatography with hexane and EtOAc
  11. customThe collected fractions afforded
  12. customan orange collected fractions

Sources & evidence

ORD record
ord-97e7f804dac649b2915dc2dc45a5da86
Source dataset
uspto-grants-2013_06
Patent number
US08471005B2

Reaction notes

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