Nitric Acid → 2-Carboxy-3-methyl-5-nitrothiophene

HRID 370094Notes

Reaction equation

HRID 370094 reaction equation
[C:1]([C:4]1[S:5][CH:6]=[CH:7][C:8]=1[CH3:9])([OH:3])=[O:2].[N+:10]([O-])([OH:12])=[O:11].C(=O)(O)[O-].[Na+]>FC(F)(F)C(O)=O>[C:1]([C:4]1[S:5][C:6]([N+:10]([O-:12])=[O:11])=[CH:7][C:8]=1[CH3:9])([OH:3])=[O:2]

Participants

5

Reactant 3

HCID 944Nitric Acid2×HCID 902693-Methyl-2-thenoic acidHCID 516892Sodium Bicarbonate

Product 1

HCID 183769572-Carboxy-3-methyl-5-nitrothiopheneYield 53%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

To a solution of 2-carboxy-3-methylthiophene (10 g, 70.3 mmol) in 80 mL of trifluoroacetic acid at 0° C. was added HNO3 (1.2 mL, 1.0 eq.) dropwise. The reaction mixture was warmed to ambient temperature and after 4 hours another 1.0 eq. of HNO3 was added. The reaction mixture was made basic with aqueous sodium bicarbonate and washed with ethyl acetate. The aqueous layer was acidified with concentrated HCl and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated in vacuo to afford 5.75 g (53%) of 2-carboxy-3-methyl-5-nitrothiophene and 2-carboxy-3-methyl-4-nitrothiophene, as a yellow solid.

Workup

  1. additionwas added
  2. washwashed with ethyl acetate
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f55eb883d1cb4b438387139eb701cfd9
Source dataset
uspto-grants-2000_10
Patent number
US06140351

Reaction notes

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