4-Aminothiophenol → Methyl 4-(4-aminophenylthio)-3-nitrobenzoate

HRID 605386Notes

Reaction equation

HRID 605386 reaction equation
Cl[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[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(O)C.C(OCC)(=O)C>[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([S:22][C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=2[N+:12]([O-:14])=[O:13])=[CH:18][CH:17]=1

Participants

6

Reactant 3

HCID 145104-AminothiophenolHCID 517045Sodium AcetateHCID 735797Methyl 4-chloro-3-nitrobenzoate

Product 1

HCID 59376804Methyl 4-(4-aminophenylthio)-3-nitrobenzoateYield 96.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of methyl 4-chloro-3-nitrobenzoate (1.00 g, 4.638 mmol) in anhydrous ethanol (40 mL) was treated with 4-aminothiophenol (0.813 g, 6.494 mmol) and anhydrous sodium acetate (1.90 g, 23.19 mmol) at room temperature under a nitrogen atmosphere, at reflux for 2 hours. The reaction was cooled, diluted with ethyl acetate (100 mL), and washed with water (3×50 mL) and brine (50 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation. The resulting orange solid was triturated with ethyl ether/hexanes (1:1 v/v, 3×30 mL), and dried in vacuo to afford the title compound (1.36 g, 4.469 mmol, 96%). 1H NMR (300 MHz, DMSO-D6) δ ppm 3.87 (s, 3 H) 5.80 (s, 2 H) 6.70 (d, J=8.46 Hz, 2 H) 7.00 (d, J=8.46 Hz, 1 H) 7.23 (d, J=8.46 Hz, 2 H) 8.05 (dd, J=8.46, 1.84 Hz, 1 H) 8.64 (d, J=1.84 Hz, 1 H). MS (ESI+) m/z 305 (M+H)+.

Workup

  1. temperatureat reflux for 2 hours
  2. temperatureThe reaction was cooled
  3. washwashed with water (3×50 mL) and brine (50 mL)
  4. dry with materialThe organic phase was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated by rotary evaporation
  7. customThe resulting orange solid was triturated with ethyl ether/hexanes (1:1 v/v, 3×30 mL)
  8. customdried in vacuo

Sources & evidence

ORD record
ord-d91ac941cb7e4e339310d3b616429717
Source dataset
uspto-grants-2011_03
Patent number
US07910595B2

Reaction notes

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