Hydrazine hydrate (1:1) → 2-amino-3-benzyloxy-N-methylaniline

HRID 613599Notes

Reaction equation

HRID 613599 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([N+:17]([O-])=O)=[C:11]([CH:14]=[CH:15][CH:16]=1)[NH:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.NN>CO>[NH2:17][C:10]1[C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:16][CH:15]=[CH:14][C:11]=1[NH:12][CH3:13]

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 107298903-benzyloxy-2-nitro-N-methylaniline

Product 1

HCID 104895412-amino-3-benzyloxy-N-methylanilineYield 87.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a mixture of 3-benzyloxy-N-methyl-2-nitroaniline (453.3 mg), 80% methanol (6.8 ml), anhydrous ferric chloride (13.6 mg) and carbon (13.6 mg) was dropwise added hydrazine monohydrate (255.6 μl) at 70° C., and the mixture was stirred for 5 hours at the same temperature. Insoluble material was filtered off, and the filtrate was concentrated in vacuo. Ethyl acetate and saturated sodium bicarbonate solution were added to the residue, and the organic layer was washed with water and brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel (ethyl acetate-n-hexane) to give 2-amino-3-benzyloxy-N-methylaniline (348.9 mg). mp: 79-81° C., NMR (CDCl3, δ): 2.87 (3H, s), 3.43 (3H, br s), 5.07 (2H, s), 6.40 (1H, d, J=7.5 Hz), 6.49 (1H, d, J=7.5 Hz), 6.80 (1H, t, J=7.5 Hz), 7.29-7.47 (5H, m).

Workup

  1. customat 70° C.
  2. filtrationInsoluble material was filtered off
  3. concentrationthe filtrate was concentrated in vacuo
  4. additionEthyl acetate and saturated sodium bicarbonate solution were added to the residue
  5. washthe organic layer was washed with water and brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by column chromatography on silica gel (ethyl acetate-n-hexane)

Sources & evidence

ORD record
ord-89e3579cf22a4c9680c702153096afa2
Source dataset
uspto-grants-1999_12
Patent number
US06008229

Reaction notes

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