tert-Butyl (2E)-but-2-enoylcarbamate → 1,1-dimethylethyl (3-{[4-(4-methyl-1H-imidazol-1-yl)phenyl]amino}butanoyl)carbamate

HRID 2366891

反応式

HRID 2366891 の反応式
[CH3:1][C:2]1[N:3]=[CH:4][N:5]([C:7]2[CH:13]=[CH:12][C:10]([NH2:11])=[CH:9][CH:8]=2)[CH:6]=1.[C:14]([NH:19][C:20](=[O:26])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])(=[O:18])/[CH:15]=[CH:16]/[CH3:17]>C(#N)C.O.O.O.O.O.O.[N+]([O-])([O-])=O.[Y+3].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O>[CH3:1][C:2]1[N:3]=[CH:4][N:5]([C:7]2[CH:13]=[CH:12][C:10]([NH:11][CH:16]([CH3:17])[CH2:15][C:14]([NH:19][C:20](=[O:26])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:18])=[CH:9][CH:8]=2)[CH:6]=1

参加物

5

反応物 2

HCID 11298363tert-Butyl (2E)-but-2-enoylcarbamateHCID 160051704-(4-Methyl-1h-imidazol-1-yl)benzenamine

生成物 1

HCID 681848641,1-dimethylethyl (3-{[4-(4-methyl-1H-imidazol-1-yl)phenyl]amino}butanoyl)carbamate収率 33%

試薬・触媒・溶媒 2

HCID 166833Yttrium (III) nitrate hexahydrate (1:3:6)触媒2 回HCID 6342Acetonitrile溶媒

反応条件

温度
50 °C

実験手順

A mixture of 4-(4-methyl-1H-imidazol-1-yl)aniline (for a preparation see Intermediate 104) (500 mg, 2.89 mmol), 1,1-dimethylethyl (2E)-2-butenoylcarbamate (for a preparation see Intermediate 105) (615 mg, 3.32 mmol) and yttrium(III) nitrate hexahydrate (111 mg, 0.289 mmol) in acetonitrile (2 mL) was heated at 50° C. for 15 h. An extra portion of yttrium(III) nitrate hexahydrate (111 mg, 0.289 mmol) was added to the mixture which was stirred for 7 more hours before being cooled to room temperature. Half of the solvent was removed in vacuo and the residue was partitioned between AcOEt (40 mL) and a saturated NaHCO3 aqueous solution (20 mL). The layers were separated and the organic phase was washed with brine (15 mL). The combined aqueous phases were extracted with AcOEt (35 mL) and the combined organic were dried over MgSO4 and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (gradient: 4 to 8% MeOH in DCM) gave a residue which was further purified by flash chromatography on silica gel (gradient: 60-95% AcOEt in Hexanes) to give 1,1-dimethylethyl (3-{[4-(4-methyl-1H-imidazol-1-yl)phenyl]amino}butanoyl)carbamate (343 mg, 0.956 mmol, 33%) as a colourless sticky solid. LCMS (method A): Retention time 0.94 min, [M+H]+=359.12

後処理

  1. temperaturebefore being cooled to room temperature
  2. customHalf of the solvent was removed in vacuo
  3. customthe residue was partitioned between AcOEt (40 mL)
  4. customThe layers were separated
  5. washthe organic phase was washed with brine (15 mL)
  6. extractionThe combined aqueous phases were extracted with AcOEt (35 mL)
  7. dry with materialthe combined organic were dried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customPurification of the residue by flash chromatography on silica gel (gradient: 4 to 8% MeOH in DCM)
  10. customgave a residue which
  11. customwas further purified by flash chromatography on silica gel (gradient: 60-95% AcOEt in Hexanes)

出典と根拠

ORDレコード
ord-1406b865db874362882fed883f74ca9f
出典データセット
uspto-grants-2014_04
特許番号
US08697725B2

関連ノート

読み込み中…