Diethyl Ether → Ethyl 5-(4-aminophenylthio)-4-nitrothiophene-2-carboxylate

HRID 883993Notes

Reaction equation

HRID 883993 reaction equation
Cl[C:2]1[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([SH:22])=[CH:18][CH:17]=1.C([O-])(=O)C.[Na+].C(OCC)C>C(O)C>[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([S:22][C:2]2[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][C:3]=2[N+:12]([O-:14])=[O:13])=[CH:18][CH:17]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 145104-AminothiophenolHCID 517045Sodium AcetateHCID 56763846HCID 56763846, compound

Product 1

HCID 67040833Ethyl 5-(4-aminophenylthio)-4-nitrothiophene-2-carboxylateYield 85%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

The product of Example 90A (1.0 g, 4.244 mmol), 4-aminothiophenol (0.797 g, 6.366 mmol), and anhydrous sodium acetate (1.74 g, 21.22 mmol) were heated in anhydrous ethanol (40 mL) under a nitrogen atmosphere at reflux for 30 minutes. The reaction was cooled to room temperature, partitioned with ethyl acetate (100 mL) and water (50 mL), separated layers, and washed organic phase with water (2×50 mL) and brine (50 mL). The organic extract was dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Trituration of the resulting solid with ethyl ether (2×30 mL) afforded the title compound as a bright yellow solid (1.167 g, 3.598 mmol, 85%). 1H NMR (300 MHz, DMSO-D6) δ ppm 1.24 (t, J=7.17 Hz, 3 H) 4.24 (q, J=7.23 Hz, 2 H) 5.94 (s, 2 H) 6.71 (d, J=8.82 Hz, 2 H) 7.35 (d, J=8.46 Hz, 2 H) 8.08 (s, 1 H); MS (ESI+) m/z 325 (M+H)+, MS (ESI−) m/z 323 (M−H)−.

Workup

  1. temperatureat reflux for 30 minutes
  2. custompartitioned with ethyl acetate (100 mL) and water (50 mL)
  3. customseparated layers
  4. washwashed organic phase with water (2×50 mL) and brine (50 mL)
  5. extractionThe organic extract
  6. dry with materialwas dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-96c2e08f10954510ae27ba026b7941ea
Source dataset
uspto-grants-2012_08
Patent number
US08236950B2

Reaction notes

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