Ammonium Chloride → Methyl 3-amino-4-((4-((tert-butoxycarbonyl)amino)phenyl)thio)benzoate

HRID 1036156Notes

Reaction equation

HRID 1036156 reaction equation
[CH3:1][O:2][C:3](=[O:28])[C:4]1[CH:9]=[CH:8][C:7]([S:10][C:11]2[CH:16]=[CH:15][C:14]([NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[CH:13][CH:12]=2)=[C:6]([N+:25]([O-])=O)[CH:5]=1.[NH4+].[Cl-]>CCO.[Fe]>[CH3:1][O:2][C:3](=[O:28])[C:4]1[CH:9]=[CH:8][C:7]([S:10][C:11]2[CH:12]=[CH:13][C:14]([NH:17][C:18]([O:20][C:21]([CH3:22])([CH3:24])[CH3:23])=[O:19])=[CH:15][CH:16]=2)=[C:6]([NH2:25])[CH:5]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 593768704-(4-tert-Butoxycarbonylamino-phenylsulfanyl)-3-nitro-benzoic acid methyl ester

Product 1

HCID 59376792Methyl 3-amino-4-((4-((tert-butoxycarbonyl)amino)phenyl)thio)benzoateYield 66.3%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Procedure

A suspension of the product from Example 1B (22.8 g, 56 mmol), Fe powder (16.4 g, 282 mmol) and NH4Cl (15.1 g, 282 mmol) in aqueous EtOH [prepared from EtOH (228 mL) and H2O (228 mL)] was gradually heated to reflux and gently refluxed for 2 hours. The reaction mixture was cooled to room temperature and filtered through celite pad. The filtrate was evaporated. The aqueous residue was portioned between Ethyl acetate and H2O, made basic to pH 9 with K2CO3, and then filtered through celite pad. The organic layer was separated, washed with H2O and brine, dried over MgSO4 and evaporated. The oily residue was crystallized in the treatment with i-Pr2O (200 mL) and stirred at room temperature for 30 minutes. The resulting crystal was collected by filtration, washed with i-Pr2O and dried at 60° C. overnight under reduced pressure gave the title compound as colorless crystal (13.9 g, 66% yield).

Workup

  1. temperaturewas gradually heated
  2. temperatureto reflux
  3. temperaturegently refluxed for 2 hours
  4. filtrationfiltered through celite pad
  5. customThe filtrate was evaporated
  6. filtrationfiltered through celite pad
  7. customThe organic layer was separated
  8. washwashed with H2O and brine
  9. dry with materialdried over MgSO4
  10. customevaporated
  11. customThe oily residue was crystallized in the treatment with i-Pr2O (200 mL)
  12. filtrationThe resulting crystal was collected by filtration
  13. washwashed with i-Pr2O
  14. customdried at 60° C. overnight under reduced pressure

Sources & evidence

ORD record
ord-58c913fbb4374ed39d7dff8650ec3f28
Source dataset
uspto-grants-2013_10
Patent number
US08546405B2

Reaction notes

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