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

HRID 883990Notes

Reaction equation

HRID 883990 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 4-(4-tert-butoxycarbonylamino-phenylsulfanyl)-3-nitro-benzoic acid methyl ester (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 AcOEt and H2O, made basic to pH 9 with K2CO3, and then filtered through celite pad. The organic layer was separated, washed with 1-120 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 to give the title compound as colorless crystal (13.9 g, 66%).

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 1-120 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-6b17f89b415047b28ee5227b914113f6
Source dataset
uspto-grants-2012_08
Patent number
US08236950B2

Reaction notes

Loading…