5-Methyl-4-nitrothiophene-2-carboxylic acid → 5-Methyl-4-nitro-thiophene-2-carboxylic acid benzyl ester

HRID 583760Notes

Reaction equation

HRID 583760 reaction equation
[CH3:1][C:2]1[S:6][C:5]([C:7]([OH:9])=[O:8])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].C(NC(=NC(C)C)O[CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)(C)C>C(#N)C>[CH2:19]([O:8][C:7]([C:5]1[S:6][C:2]([CH3:1])=[C:3]([N+:10]([O-:12])=[O:11])[CH:4]=1)=[O:9])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

4

Reactant 2

HCID 31107845-Methyl-4-nitrothiophene-2-carboxylic acidHCID 11128254o-Benzyl-n,n'-diisopropylisourea

Product 1

HCID 381853005-Methyl-4-nitro-thiophene-2-carboxylic acid benzyl esterYield 81.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A mixture of 5-methyl-4-nitro-thiophene-2-carboxylic acid (1.0 g, 5.3 mmol) and 1,3-diisopropyl-2-benzylisourea (1.54 g, 6.4 mmol) in acetonitrile (25 mL) was stirred under an inert atmosphere and heated to reflux. After 48 hours the mixture was cooled, the solvent was removed under reduced pressure, and the residue was triturated in diethyl ether and cooled. The precipitate was filtered off and rinsed with cold ether. The filtrate and washings were combined, and rotary evaporated under reduced pressure. The resulting residue was dissolved in a minimum of ethyl acetate, and the solution was filtered through a column of silica gel, eluting with more ethyl acetate. The filtrate was rotary evaporated to dryness under reduced pressure to afford 1.2 g of 5-methyl-4-nitro-thiophene-2-carboxylic acid benzyl ester. A sample was chromatographed on silica gel in ether/petroleum ether 1:1, then recrystallized from ethanol to give product with a mp 57-58° C.

Workup

  1. temperatureheated to reflux
  2. temperatureAfter 48 hours the mixture was cooled
  3. customthe solvent was removed under reduced pressure
  4. customthe residue was triturated in diethyl ether
  5. temperaturecooled
  6. filtrationThe precipitate was filtered off
  7. washrinsed with cold ether
  8. customrotary evaporated under reduced pressure
  9. dissolutionThe resulting residue was dissolved in a minimum of ethyl acetate
  10. filtrationthe solution was filtered through a column of silica gel
  11. washeluting with more ethyl acetate
  12. customThe filtrate was rotary evaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-4f322d3999a647b4915d486f752b59ee
Source dataset
uspto-grants-2005_08
Patent number
US06924276B2

Reaction notes

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