Hydrazine hydrate (1:1) → 5-Methoxy-o-toluidine

HRID 2409472Notes

Reaction equation

HRID 2409472 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[C:5]([N+:10]([O-])=O)[CH:4]=1.O.NN>COCCOC.[Pd]>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[C:5]([CH:4]=1)[NH2:10]

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)2×HCID 871374-Methyl-3-nitroanisole

Product 1

HCID 995005-Methoxy-o-toluidine

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a solution of 4-methoxy-1-methyl-2-nitrobenzene (18.0 g, 108 mmol) in 160 mL of DME was added Pd/C (10%, 0.9 g) under nitrogen. Then hydrazine hydrate (16.17 g, 323 mmol) was added dropwise. The mixture was heated and stirred under reflux for 4 h. Then another 3 mL of hydrazine hydrate was added and stirred under reflux for 2d. Then the reaction mixture was cooled to RT, filtered through celite and evaporated to dryness to give 5-methoxy-2-methylaniline as yellow oil that solidified upon drying under vacuum to give 14.8 g (100%). 1H NMR (300 MHz, CDCl3): δ 6.94 (d, J=7.53 Hz, 1H), 6.28 (d, J=7.53 Hz, 1H), 6.26 (s, 1H), 3.78 (s, 3H), 3.5 (br, 1H), 2.10 (s, 3H), 1.6 (br, 1H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 4 h
  3. stirringstirred
  4. filtrationfiltered through celite
  5. customevaporated to dryness

Sources & evidence

ORD record
ord-dd6ac3f633134437affbdcf5249eb608
Source dataset
uspto-grants-2014_08
Patent number
US08815906B2

Reaction notes

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