Formic Acid → dimethyl 4-nitroisophthalate
Reaction equation
[CH:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[N+:13]([O-:15])=[O:14])[C:6]([O:8][CH3:9])=[O:7])=[O:2].OO.[CH:18](O)=[O:19]>>[N+:13]([C:12]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:1]([O:19][CH3:18])=[O:2])([O-:15])=[O:14]Participants
Procedure
To a stirred solution of methyl 3-formyl-4-nitrobenzoate (1.5 g, 7.18 mmol) in formic acid (2 mL) was added hydrogen peroxide (2.5 mL, 30% in water). The reaction mixture was stirred at r.t. for 16 h. Additional hydrogen peroxide (2.5 mL, 30% in water) was added, and the reaction mixture stirred at r.t. for 8 h before being concentrated in vacuo. The residue was dissolved in 2% HCl in MeOH (40 mL). The solution was stirred at 70° C. for 4 days, then concentrated in vacuo. The residue was dissolved in DCM (10 mL), and the solution washed with aqueous sat. NaHCO3 (2×10 mL), dried (MgSO4), filtered and concentrated in vacuo to give the title compound (1.52 g, 87%) as a colourless oil. δH (CDCl3) 8.43 (1H, s), 8.29 (1H, dd, J 1.8 and 8.6 Hz), 7.92 (1H, d, J 8.3 Hz), 3.99 (3H, s), 3.95 (3H, s). LCMS (ES+) 240.0 (M+H)+, RT 1.80 minutes (Method 12).
Workup
- stirringthe reaction mixture stirred at r.t. for 8 h
- concentrationbefore being concentrated in vacuo
- dissolutionThe residue was dissolved in 2% HCl in MeOH (40 mL)
- stirringThe solution was stirred at 70° C. for 4 days
- concentrationconcentrated in vacuo
- dissolutionThe residue was dissolved in DCM (10 mL)
- washthe solution washed with aqueous sat. NaHCO3 (2×10 mL)
- dry with materialdried (MgSO4)
- filtrationfiltered
- concentrationconcentrated in vacuo
Sources & evidence
- ORD record
- ord-6bd1473e62ed44d6bbc4b2975475d2a1
- Source dataset
- uspto-grants-2012_08
- Patent number
- US08242116B2
Reaction notes
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