Methyl 4-cyano-2-methoxybenzoate → Methyl 4-(aminomethyl)-2-methoxybenzoate

HRID 1807261Notes

Reaction equation

HRID 1807261 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[N:11])=[CH:6][C:5]=1[O:12][CH3:13]>CO.[Ni]>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][NH2:11])=[CH:6][C:5]=1[O:12][CH3:13]

Participants

4

Reactant 1

HCID 57426183Methyl 4-cyano-2-methoxybenzoate

Product 1

HCID 67094960Methyl 4-(aminomethyl)-2-methoxybenzoateYield 37.4%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

A solution of 4-cyano-2-methoxy benzoic acid (1.0 g, 5.65 mmol, Biogene) in methanol was reacted with p-toluenesulfonic acid monohydrate (285.6 mg, 1.479 mmol) and heated to reflux for 16 hrs. The solvent was removed and the reaction residue was extracted with EtOAc, and washed with saturated sodium carbonate, water, and saturated NaCl, and dried over Na2SO4 to give 4-Cyano-2-methoxy-benzoic acid methyl ester (1.04 g, 96%). This ester (1.01 g, 5.28 mmol) in methanol (50 mL) was reacted with Raney Ni (3 spatula tips full, exact amount unknown, Aldrich) under 50 psi H2 in a Parr apparatus for 16 hrs. After filtering through Celite and concentrating, the crude mixture was purified by silica gel chromatography using methanol and methylene chloride to give 4-aminomethyl-2-methoxy-benzoic acid methyl ester (385.7 mg, 37%).

Workup

  1. filtrationAfter filtering through Celite
  2. concentrationconcentrating
  3. customthe crude mixture was purified by silica gel chromatography

Sources & evidence

ORD record
ord-1091679f84ff45c5b24764c2a9390693
Source dataset
uspto-grants-2013_01
Patent number
US08354444B2

Reaction notes

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