Oxalic Acid → Tert-butyl [2-(aminomethyl)phenyl]acetate oxalate salt
Reaction equation
[C:1]([O:5][C:6](=[O:18])[CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH2:14][N:15]=[N+]=[N-])([CH3:4])([CH3:3])[CH3:2].[C:19]([OH:24])(=[O:23])[C:20]([OH:22])=[O:21]>C(OC)(C)(C)C.[Pd]>[C:19]([OH:24])(=[O:23])[C:20]([OH:22])=[O:21].[NH2:15][CH2:14][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=1[CH2:7][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:18]Participants
Procedure
To a solution of 78.0 g (0.312 mol) 2-azidomethylphenylacetic acid t-butyl ester in 1.36 L TBF was added 7.8 g (50% water wet) 5% Pd on C and the mixture shaken mechanically in a 2 L heavy-walled flask under H2 at 45 psi for 2 h. The catalyst was removed by filtration through a bed of celite, rinsing with 250 mL THF. To the filtrate was added a solution of 31.25 g (0.347 mol) oxalic acid in 500 mL methyl tert-butyl ether, and the resultant suspension stirred at room temperature for 30 min. The solid was collected on a filter and washed with 300 mL methyl tert-butyl ether (the filtration was very slow, requiring about 3 hours). Drying under reduced pressure at 60° C. for 18 h gave 42.4 g (39% overall from 2-bromomethylphenylacetic acid) tert-butyl [2-(aminomethyl)phenyl]acetate oxalate salt as a white powder. The product is unstable as the free base, and will cyclize to the amide over several hours at room temperature.
Workup
- customThe catalyst was removed by filtration through a bed of celite
- washrinsing with 250 mL THF
- customThe solid was collected on
- filtrationa filter
- washwashed with 300 mL methyl tert-butyl ether (
- filtrationthe filtration
- waitrequiring about 3 hours
- customDrying under reduced pressure at 60° C. for 18 h
Sources & evidence
- ORD record
- ord-0ef8919af7f34237ae4346aee4b8a73f
- Source dataset
- uspto-grants-2003_08
- Patent number
- US06610701B2
Reaction notes
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