Ammonium Hydroxide → t-Butyl [3-(aminomethyl)phenoxy]acetate

HRID 2300570Notes

Reaction equation

HRID 2300570 reaction equation
[C:1]([O:5][C:6](=[O:18])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH:15]=[N:16]O)[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[OH-].[NH4+]>CCO.[Ni]>[C:1]([O:5][C:6](=[O:18])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][NH2:16])[CH:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 14923Ammonium HydroxideHCID 73704862(3-(Hydroxyimino-methyl)-phenoxy)-acetic acid tert-butyl ester

Product 1

HCID 20758042t-Butyl [3-(aminomethyl)phenoxy]acetate

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent3×

Procedure

To a solution of (3-(hydroxyimino-methyl)-phenoxy)-acetic acid tert-butyl ester prepared of Preparation 20, Step B (2.25 g, 5.96 mmol) in EtOH (10 mL) was added Raney Nickel (about 1 g, washed with water followed by EtOH) in 100 mL EtOH. Additional EtOH (90 mL) was required for the transfer. Ammonium hydroxide (10 mL) was added and the mixture was shaken under 45 psi for H2 for 4 hours. The catalyst was removed via filtration through Celite® and the solution was concentrated to a clear oil. Purification via flash chromatography on silica gel (96.5/3.5/0.1 to 9/1/0.1 CH2Cl2/MeOH/NH4OH) afforded the title compound as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.23 (m, 1H), 6.92 (m, 2H), 6.72 (d, 1H), 4.50 (s, 2H), 3.82 (s, 2H), 1.96 (m, 2H), 1.46 (s, 9H); MS 238 (M+1).

Workup

  1. customThe catalyst was removed via filtration through Celite®
  2. concentrationthe solution was concentrated to a clear oil
  3. customPurification via flash chromatography on silica gel (96.5/3.5/0.1 to 9/1/0.1 CH2Cl2/MeOH/NH4OH)

Sources & evidence

ORD record
ord-1935ba8a419741f6a4bd64d3567ba767
Source dataset
uspto-grants-2002_12
Patent number
US06498172B1

Reaction notes

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