Hydrazine → (2-Amino-6-bromo-benzyl)-methyl-carbamic acid tert-butyl ester

HRID 901863Notes

Reaction equation

HRID 901863 reaction equation
[C:1]([O:5][C:6](=[O:20])[N:7]([CH2:9][C:10]1[C:15]([N+:16]([O-])=O)=[CH:14][CH:13]=[CH:12][C:11]=1[Br:19])[CH3:8])([CH3:4])([CH3:3])[CH3:2].NN>>[C:1]([O:5][C:6](=[O:20])[N:7]([CH2:9][C:10]1[C:11]([Br:19])=[CH:12][CH:13]=[CH:14][C:15]=1[NH2:16])[CH3:8])([CH3:4])([CH3:2])[CH3:3]

Participants

3

Reactant 2

HCID 9321HydrazineHCID 58824120(2-Bromo-6-nitro-benzyl)-methyl-carbamic acid tert-butyl ester

Product 1

HCID 58824133(2-Amino-6-bromo-benzyl)-methyl-carbamic acid tert-butyl esterYield 69%

Procedure

To a warm solution of (2-bromo-6-nitro-benzyl)-methyl-carbamic acid tert-butyl ester from Preparation 2 (589 mg, 1.71 mmol), and a small (catalytic) amount of Ra(Ni) in TBF/MeOH (8 ml/9 ml) was added H2NNH2 (110 μl, 3.5 mmol). With stirring, the solution was heated under reflux for an hour and was allowed to cool to room temperature. The reaction mixture was filtered through celite and washed with ethyl acetate. The concentrated filtrate was purified by flash chromatography to give (2-amino-6-bromo-benzyl)-methyl-carbamic acid tert-butyl ester (371 mg, 69%). 1H NMR (CDCl3, 300 MHz) δ: 1.48(s, 9H), 2.80(s, 3H), 4.67(s, 2H); 6.56(m,1H), 6.90(m, 2H).

Workup

  1. temperaturethe solution was heated
  2. temperatureunder reflux for an hour
  3. filtrationThe reaction mixture was filtered through celite
  4. washwashed with ethyl acetate
  5. customThe concentrated filtrate was purified by flash chromatography

Sources & evidence

ORD record
ord-ec141cbe60334ce4924416b44d748f45
Source dataset
uspto-grants-2008_04
Patent number
US07365063B2

Reaction notes

Loading…