Diethyl Ether → HCID 11430818, compound

HRID 1025667Notes

Reaction equation

HRID 1025667 reaction equation
[CH:1]([N-:4]C(C)C)(C)C.[Li+].[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]2[CH:20]=[C:19]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[N:18]=[C:17]2[C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:29]=2[Cl:35])=[CH:12][CH:11]=1.C1(C)C=CC(S(C#N)(=O)=O)=CC=1.C(OCC)C>C1COCC1>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]2[C:20]([C:1]#[N:4])=[C:19]([C:21]([O:23][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:22])[N:18]=[C:17]2[C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:29]=2[Cl:35])=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 87946p-Toluenesulphonyl cyanideHCID 2724682Lithium diisopropylamideHCID 11270197tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate

Product 1

HCID 11430818HCID 11430818, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Lithium diisopropyl amide (LDA) (5.25 mL of a 2 M solution in THF, 0.0105 mol) is added dropwise to a cooled solution (−70° C.) of tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate (4.24 gram, 0.010 mol) in anhydrous THF (80 mL) in a nitrogen atmosphere and the resulting mixture is stirred for one hour. A solution of p-toluenesulfonyl cyanide (1.88 gram, 0.011 mol) in anhydrous THF (20 mL) is added dropwise and the resulting red solution is stirred for one hour at −70° C. and then allowed to attain room temperature. Diethyl ether is added and the resulting solution is quenched with water and filtered over hyflo. The organic layer is collected and washed with water, dried over MgSO4, filtered and concentrated in vacuo to give an oil. This oil is purified by column chromatography (dichloromethane, silicagel) to give 3.4 gram of tert-butyl 1-(4-chlorophenyl)-5-cyano-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate. Recrystallisation from diisopropyl ether gave crystalline tert-butyl 1-(4-chlorophenyl)-5-cyano-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate (2.57 gram, 57% yield). Melting point: 210-212° C.

Workup

  1. stirringthe resulting red solution is stirred for one hour at −70° C.
  2. customto attain room temperature
  3. customthe resulting solution is quenched with water
  4. filtrationfiltered over hyflo
  5. customThe organic layer is collected
  6. washwashed with water
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give an oil
  11. customThis oil is purified by column chromatography (dichloromethane, silicagel)

Sources & evidence

ORD record
ord-c6fcd00b651d41518cbd238fb6125b29
Source dataset
uspto-grants-2014_05
Patent number
US08729101B2

Reaction notes

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