Methanol → 4-Ethoxy-2-methylaniline

HRID 2174513Notes

Reaction equation

HRID 2174513 reaction equation
[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-])=O)=[C:6]([CH3:13])[CH:5]=1)[CH3:2].CO>CCOC(C)=O.[Pd]>[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([NH2:10])=[C:6]([CH3:13])[CH:5]=1)[CH3:2]

Participants

5

Reactant 2

HCID 887MethanolHCID 115645664-Ethoxy-2-methyl-1-nitrobenzene

Product 1

HCID 167847184-Ethoxy-2-methylanilineYield 92%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Compound 404a (250 mg, 1.38 mmol) was dissolved in EtOAc (10 mL) and MeOH (10 mL) and transferred to a 250 mL hydrogenation flask. 10% Pd/C (25 mg, 10% w/w) was added and the sample was hydrogenated for 4 h at 35 psi H2. Upon completion, the mixture was filtered over a bed of Celite and then concentrated in vacuo. The residue was dissolved in EtOAc (50 mL) and washed with NaHCO3 (50 mL×3). The organic layer was dried over Na2SO4 to yield a dark-red oil (192 mg, 92%): TLC Rf 0.30 (20% EtOAc/hexanes). 1NMR (600 MHz, CDCl3) δ 6.67 (s, 1H), 6.62 (m, 2H), 3.97-3.93 (q, 2H, J=6.96 Hz), 3.42 (s, 2H), 2.16 (s, 3H), 1.38-1.35 (t, 3H, J=7.02 Hz). NMR (150 MHz, CDCl3) δ 152.3, 138.1, 124.4, 117.45, 116.34, 113.1, 64.2, 17.9, 15.2. Elemental analysis calculated for C9H13NO: C, 71.49; H, 8.67; N, 9.26. Found: C, 71.42; H, 8.76; N, 9.04.

Workup

  1. filtrationUpon completion, the mixture was filtered over a bed of Celite
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in EtOAc (50 mL)
  4. washwashed with NaHCO3 (50 mL×3)
  5. dry with materialThe organic layer was dried over Na2SO4

Sources & evidence

ORD record
ord-c897b0a7137b4163835ef4891417185a
Source dataset
uspto-grants-2015_06
Patent number
US09061994B1

Reaction notes

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