Iodoethane → HCID 67185128、化合物

HRID 1843633

反応式

HRID 1843633 の反応式
[CH2:1]([N:8]([CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:9]1[CH:14]=[CH:13][C:12]([F:15])=[C:11]([C:16]2[C:20]([C:21]3[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=3)=[CH:19][NH:18][N:17]=2)[C:10]=1[F:27])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].[CH2:37](I)[CH3:38]>C(Cl)Cl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH2:28]([N:8]([CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:9]1[CH:14]=[CH:13][C:12]([F:15])=[C:11]([C:16]2[C:20]([C:21]3[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=3)=[CH:19][N:18]([CH2:37][CH3:38])[N:17]=2)[C:10]=1[F:27])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1

参加物

7

反応物 3

HCID 6340IodoethaneHCID 14798Sodium HydroxideHCID 178505869HCID 178505869、化合物

生成物 1

HCID 67185128HCID 67185128、化合物収率 52%

試薬・触媒・溶媒 3

HCID 74236Tetrabutylammonium Bromide触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回

実験手順

Dibenzyl[2,4-difluoro-3-(4-pyridin-4-yl-1H-pyrazol-3-yl)-phenyl]-amine (prepared as described in Example 22) (4 g, 8.84 mmol) was suspended in DCM (44 mL) and 32% NaOH (44 mL) was added followed by tetrabutylammonium bromide (400 mg, 1.24 mmol, 0.14 eq). Neat ethyliodide (1.07 mL, 13.27 mmol, 1.5 eq) was then added and the biphasic mixture was vigorously stirred at room temperature for 1 h. By HPLC analysis at 254 nm the regioisomeric ratio was 55:45 in favour of the most polar N1-substituted pyrazole. The reaction mixture was then diluted with water (50 mL) and DCM (50 mL) and the two layers were separated. Aqueous phase was extracted with DCM (2×50 mL) and combined organic layers were washed with water (2×50 mL) and brine (50 mL), dried over Na2SO4 and evaporated to dryness. The two reagioisomers were separated by flash chromatography on silica gel (n-hexane/ethyl acetate 1:1) and the desired N1-ethylpyrazole was obtained as a white solid in 52% yield.

後処理

  1. customthe two layers were separated
  2. extractionAqueous phase was extracted with DCM (2×50 mL)
  3. washwere washed with water (2×50 mL) and brine (50 mL)
  4. dry with materialdried over Na2SO4
  5. customevaporated to dryness
  6. customThe two reagioisomers were separated by flash chromatography on silica gel (n-hexane/ethyl acetate 1:1)

出典と根拠

ORDレコード
ord-e6c063344d5b42998b92e504966d8beb
出典データセット
uspto-grants-2015_02
特許番号
US08946250B2

関連ノート

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