Ammonium Chloride → Tert-butyl 3-amino-4-chlorobenzylcarbamate
Reaction equation
[Cl:1][C:2]1[CH:16]=[CH:15][C:5]([CH2:6][NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[CH:4][C:3]=1[N+:17]([O-])=O.[NH4+].[Cl-]>[Fe].CCO>[NH2:17][C:3]1[CH:4]=[C:5]([CH:15]=[CH:16][C:2]=1[Cl:1])[CH2:6][NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:11])[CH3:12]Participants
5
Reactant 2
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 90 °C
Procedure
A mixture of tert-butyl 4-chloro-3-nitrobenzylcarbamate (crude material from step (b)), Fe powder (17.65 g, 316 mmol), NH4Cl (aq, sat, 100 mL) and EtOH (100 mL) was heated at 90° C. for 4 h and allowed to cool. The pH was adjusted to −10 and the mixture was filtered through Celite. The solids were washed with EtOAc and EtOH and the combined filtrates concentrated to remove the organic solvents. The residue was added to ammonia and the mixture was extracted with DCM. The combined extracts were washed with brine, dried over Na2SO4 and concentrated. Crystallization from EtOAc/petroleum ether gave the sub-title compound. Yield: 15.5 g (75% from 4-chloro-3-nitrobenzylamine).
Workup
- temperatureto cool
- filtrationthe mixture was filtered through Celite
- washThe solids were washed with EtOAc and EtOH
- concentrationthe combined filtrates concentrated
- customto remove the organic solvents
- additionThe residue was added to ammonia
- extractionthe mixture was extracted with DCM
- washThe combined extracts were washed with brine
- dry with materialdried over Na2SO4
- concentrationconcentrated
- customCrystallization from EtOAc/petroleum ether
Sources & evidence
- ORD record
- ord-67f599a34f7e4cc4b761f03100a27213
- Source dataset
- uspto-grants-2014_12
- Patent number
- US08921405B2
Reaction notes
Loading…