4-Bromoaniline → HCID 68872521, compound

HRID 1782097Notes

Reaction equation

HRID 1782097 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[C:9]([O:13][CH2:14][CH3:15])(=[O:12])[CH:10]=O.S([CH2:26][N+:27]#[C-:28])(C1C=CC(C)=CC=1)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>CO.O>[Br:1][C:2]1[CH:8]=[CH:7][C:5]([N:6]2[C:10]([C:9]([O:13][CH2:14][CH3:15])=[O:12])=[CH:28][N:27]=[CH:26]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 78074-BromoanilineHCID 11430Potassium CarbonateHCID 70211Ethyl oxoacetateHCID 161915Tosylmethyl isocyanide

Product 1

HCID 68872521HCID 68872521, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

To a solution of 4-bromoaniline (8.6 g, 50 mmol) in MeOH (100 mL) was added ethyl glyoxalate (12 mL, 60 mmol, 50% in toluene) and the resulting mixture heated at reflux for 3.5 h. The mixture was then concentrated in vacuo and the resulting residue reconstituted in anhydrous ethanol (100 mL) and treated with tosylmethyl isocyanide (14.6 g, 75 mmol) and potassium carbonate (13.8 g, 100 mmol). The resulting mixture was heated at 65° C. for 4 h, then cooled to rt and poured to water (500 mL) and the resulting solid collected by filtration. The crude material thus isolated was crystallized from ethyl acetate/hexane to give pure 3-(4-bromophenyl)-3H-imidazole-4-carboxylic acid ethyl ester (4). MS (ES+): m/z 295/297 (1/1) [MH+]. 1H NMR (CDCl3, 400 MHz): δ=1.27 (t, J=7.1 Hz, 3H), 4.22 (q, J=7.1 Hz, 2H), 7.22 (d, J=8.7 Hz, 2H), 7.61 (d, J=8.7 Hz, 2H), 7.65 (d, J=0.9 Hz, 1H) and 7.85 (d, J=0.9 Hz, 1H).

Workup

  1. temperaturethe resulting mixture heated
  2. temperatureat reflux for 3.5 h
  3. concentrationThe mixture was then concentrated in vacuo
  4. temperaturecooled to rt
  5. filtrationthe resulting solid collected by filtration
  6. customThe crude material thus isolated
  7. customwas crystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-656fa2eeb7774f56b51c184b681db2d5
Source dataset
uspto-grants-2009_03
Patent number
US07498354B2

Reaction notes

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