Toluene → Tert-butyl 4-(methoxycarbonyl)-3-nitrobenzoate

HRID 965275Notes

Reaction equation

HRID 965275 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([C:10]([OH:12])=[O:11])=[CH:6][C:5]=1[N+:13]([O-:15])=[O:14].C(Cl)(=O)C(Cl)=O.[C:23]1([CH3:29])[CH:28]=CC=C[CH:24]=1>CN(C=O)C.C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([C:10]([O:12][C:23]([CH3:29])([CH3:28])[CH3:24])=[O:11])=[CH:6][C:5]=1[N+:13]([O-:15])=[O:14]

Participants

6

Reactant 3

HCID 1140TolueneHCID 65578Oxalyl chlorideHCID 98592Methyl hydrogen 2-nitroterephthalate

Product 1

HCID 23291046Tert-butyl 4-(methoxycarbonyl)-3-nitrobenzoateYield 83%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred suspension of the above acid ((6), 7.0 g, 31 mMol) in toluene (25 mL) was added oxalylchloride (5 mL) followed by one drop of dry DMF. After stirring for 16 h (the solution became clear after ~30 minutes) the reaction was evaporated to dryness and re-evaporated from fresh toluene (2×100 mL). To the resulting acid chloride in CHCl3 (10 mL) with stirring at 0° C. was added t-BuOH (1 mL) followed by pyridine (0.6 mL). The reaction was allowed to warm to room temperature and stirred for 6 h. The resulting reaction was stripped of solvent, taken up in ethyl acetate, washed with aq. 1N NaHCO3, brine, dried (MgSO4) and evaporated under reduced pressure. Purification by flash chromatography on silica gel eluted with 10% ethyl acetate in hexane gave product (7) (7.28 g, 83%) as a clear oil.

Workup

  1. waitbecame clear after ~30 minutes
  2. custom) the reaction was evaporated to dryness
  3. customre-evaporated from fresh toluene (2×100 mL)
  4. stirringTo the resulting acid chloride in CHCl3 (10 mL) with stirring at 0° C.
  5. additionwas added t-BuOH (1 mL)
  6. stirringstirred for 6 h
  7. customThe resulting reaction
  8. washwashed with aq. 1N NaHCO3, brine
  9. dry with materialdried (MgSO4)
  10. customevaporated under reduced pressure
  11. customPurification by flash chromatography on silica gel
  12. washeluted with 10% ethyl acetate in hexane

Sources & evidence

ORD record
ord-cc3ce8af49464841adb81265b3a8f541
Source dataset
uspto-grants-1998_06
Patent number
US05773512

Reaction notes

Loading…