Ethylenediamine → 2-(4,5-dihydro-1H-imidazol-2-yl)-6-methoxyaniline

HRID 536220Notes

Reaction equation

HRID 536220 reaction equation
[NH2:1][C:2]1[C:9]([O:10][CH3:11])=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[S].[CH2:13](N)[CH2:14][NH2:15]>>[NH:5]1[CH2:13][CH2:14][N:15]=[C:4]1[C:3]1[CH:6]=[CH:7][CH:8]=[C:9]([O:10][CH3:11])[C:2]=1[NH2:1]

Participants

4

Reactant 3

HCID 3301EthylenediamineHCID 5362487SulfurHCID 118191992-amino-3-methoxybenzonitrile

Product 1

HCID 583773572-(4,5-dihydro-1H-imidazol-2-yl)-6-methoxyanilineYield 50%

Conditions

Temperature
60 °C

Procedure

2-Amino-3-methoxybenzonitrile (Step 2, 26.6 g, 179 mmol) was suspended in ethylenediamine (250 mL) and degassed thoroughly. To this was added sulfur powder (8 g, 251 mmol) slowly, then the reaction was heated to 60° C. and stirred 5 h. The reaction was then cooled, concentrated under reduced pressure, then treated with water (300 mL). The resulting suspension was collected by vacuum filtration and washed with water. The solid was purified via silica gel chromatography (50-100% EtOAc/hexanes). Fractions containing product were combined, the solvent removed under reduced pressure to give the title compound (17.3 g, 50%): HPLC MS RT=1.05 min, MH+=192.1; 1H NMR (DMSO-d6) δ: 3.81 (3H, s), 3.90 (4H, s), 6.65 (1H, t), 6.86 (1H, dd), 7.03 (1H, dd).

Workup

  1. customdegassed thoroughly
  2. temperatureThe reaction was then cooled
  3. concentrationconcentrated under reduced pressure
  4. additiontreated with water (300 mL)
  5. filtrationThe resulting suspension was collected by vacuum filtration
  6. washwashed with water
  7. customThe solid was purified via silica gel chromatography (50-100% EtOAc/hexanes)
  8. additionFractions containing product
  9. customthe solvent removed under reduced pressure

Sources & evidence

ORD record
ord-f950c1a1a3174c25b4e8bf54973fbc7b
Source dataset
uspto-grants-2014_10
Patent number
US08859572B2

Reaction notes

Loading…