4-Iodoaniline → HCID 68546506, compound

HRID 1446069Notes

Reaction equation

HRID 1446069 reaction equation
Br[C:2]1[N:3]([CH2:10][C:11]2([CH3:14])[CH2:13][O:12]2)[CH:4]=[C:5]([N+:7]([O-:9])=[O:8])[N:6]=1.[I:15][C:16]1[CH:22]=[CH:21][C:19]([NH2:20])=[CH:18][CH:17]=1>C(#N)C.O.O.O.O.O.O.[Co](Cl)Cl>[I:15][C:16]1[CH:22]=[CH:21][C:19]([NH:20][CH2:13][C:11]2([CH3:14])[O:12][C:2]3=[N:6][C:5]([N+:7]([O-:9])=[O:8])=[CH:4][N:3]3[CH2:10]2)=[CH:18][CH:17]=1

Participants

5

Reactant 2

HCID 108934-IodoanilineHCID 85107489HCID 85107489, compound

Product 1

HCID 68546506HCID 68546506, compoundYield 11.2%

Reagents, catalysts & solvents 2

HCID 517166Dichlorocobalt hexahydrateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

2-Bromo-1-(2-methyl-oxiranylmethyl)-4-nitro-1H-imidazole (prepared as described by Goto, F.; et al: WO 2004035547; 0.54 g, 2 mmol), 4-iodoaniline (1.31 g, 6 mmol) and cobalt (II) chloride hexahydrate were suspended in 15 mL acetonitrile and stirred at 60° C. for 3 hours. The resulting mixture was filtered through a Celite pad and washed with EtOAc. Upon removing solvent, brown solid precipitated out. The precipitate (˜200 mg) was dried and dissolved in 5 mL DMF. The solution was cooled to −78° C. before NaH (20 mg, 60% in mineral oil) was added quickly. The resulting mixture was warmed up to room temperature and stirred for one hour, before it was quenched with 1 mL water and partitioned in 50 mL EtOAc/50 mL water. The organic layer was washed with brine and dried over Na2SO4. The concentrated residue was purified by aolumn chromatography (EtOAc/Hexanes, v/v, 1/1 to 4/1) to give the titled product (90 mg) as yellow solid. ESI MS m/z 401 (M+H). 1H NMR (400 MHz, MeCN-d3) δ 7.66 (s, 1H), 7.39 (d, J=5.2 Hz, 2H), 6.52 (d, J=5.2 Hz, 2H), 4.75-4.91 (m, 1H), 4.20 (d, J=10.4 Hz, 1H), 4.02 (d, J=10.4 Hz, 1H), 3.37-3.58 (m, 2H), 1.63 (s, 3H).

Workup

  1. filtrationThe resulting mixture was filtered through a Celite pad
  2. washwashed with EtOAc
  3. customUpon removing solvent, brown solid
  4. customprecipitated out
  5. dry with materialThe precipitate (˜200 mg) was dried
  6. dissolutiondissolved in 5 mL DMF
  7. temperatureThe solution was cooled to −78° C. before NaH (20 mg, 60% in mineral oil)
  8. additionwas added quickly
  9. temperatureThe resulting mixture was warmed up to room temperature
  10. stirringstirred for one hour, before it
  11. customwas quenched with 1 mL water
  12. custompartitioned in 50 mL EtOAc/50 mL water
  13. washThe organic layer was washed with brine
  14. dry with materialdried over Na2SO4
  15. customThe concentrated residue was purified by aolumn chromatography (EtOAc/Hexanes, v/v, 1/1 to 4/1)

Sources & evidence

ORD record
ord-3fa2569d8a9a437b96614c2cde7f2469
Source dataset
uspto-grants-2010_02
Patent number
US07666864B2

Reaction notes

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