Diethyl Ether → tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-5-cyano-1H-imidazole-4-carboxylate

HRID 1025667ノート

反応式

HRID 1025667 の反応式
[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

参加物

6

反応物 4

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

生成物 1

HCID 11430818tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-5-cyano-1H-imidazole-4-carboxylate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-c6fcd00b651d41518cbd238fb6125b29
出典データセット
uspto-grants-2014_05
特許番号
US08729101B2

反応ノート

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