Methyl 2-(4-nitrophenoxy)propanoate → Methyl 2-(4-aminophenoxy)propanoate

HRID 83782Notes

Reaction equation

HRID 83782 reaction equation
[CH3:1][O:2][C:3](=[O:16])[CH:4]([O:6][C:7]1[CH:12]=[CH:11][C:10]([N+:13]([O-])=O)=[CH:9][CH:8]=1)[CH3:5]>CN(C)C=O.[Ni]>[CH3:1][O:2][C:3](=[O:16])[CH:4]([O:6][C:7]1[CH:12]=[CH:11][C:10]([NH2:13])=[CH:9][CH:8]=1)[CH3:5]

Participants

4

Reactant 1

HCID 4501947Methyl 2-(4-nitrophenoxy)propanoate

Product 1

HCID 22060471Methyl 2-(4-aminophenoxy)propanoateYield 86.55%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 6228DimethylformamideSolvent

Procedure

Method-A Through a mixture of 2-(4-aminophenoxy)-propionic acid 9 (240 g, 1.103 mmol) in methanol (4.8 liters) was passed dry HCl gas at 10° C. for 1 hour followed by reflux for 48 hours. Methanol (2.5 liter) was distilled off, ice water (1 liter) was added and the pH was adjusted to 7.5 with K2CO3. Crude 10 was extracted into chloroform, washed with 5% NaHCO3 solution, water, dried over Na2SO4 and distilled to give 10 (80 g, 37.2%) as a brown syrup. Method-B 2-(4-Nitrophenoxy)-propionic acid methyl ester 14 (20 g, 88.88 mmol) was dissolved in dimethyl formamide (100 ml) in a pressure vessel, Raney nickel (20 grams) was added and the mixture stirred under an atmosphere of hydrogen (4 kg) for 6 hours. The catalyst was removed by filtration and the dimethyl formamide distilled off under vacuum. Crude 10 was purified by column chromatography on silica gel using chloroform as eluant to get pure 10 (15 g, 86.55%) as a brown syrup.

Workup

  1. customThe catalyst was removed by filtration
  2. distillationthe dimethyl formamide distilled off under vacuum
  3. customCrude 10 was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-ce083270d03e4b0487e2c288685bc83c
Source dataset
uspto-grants-2014_09
Patent number
US08846845B2

Reaction notes

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