Acetic Acid → 3-tert-Butyl-1-(2-methylphenyl)-1H-pyrazol-5-amine

HRID 915558

反応式

HRID 915558 の反応式
[CH3:1][C:2]([CH3:9])([CH3:8])[C:3](=O)[CH2:4][C:5]#[N:6].Cl.[CH3:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[NH:18][NH2:19].C(O)(=O)C.C(=O)(O)[O-].[Na+]>C(O)C.CCCCCC>[C:2]([C:3]1[CH:4]=[C:5]([NH2:6])[N:18]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2[CH3:11])[N:19]=1)([CH3:9])([CH3:8])[CH3:1]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 71554o-Tolylhydrazinium(1+) chlorideHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 516892Sodium Bicarbonate

生成物 1

HCID 7706433-tert-Butyl-1-(2-methylphenyl)-1H-pyrazol-5-amine収率 93%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 8058Hexane溶媒

実験手順

4,4-Dimethyl-3-oxopentanenitrile (36.7 g, 0.29 mol), (2-methylphenyl)hydrazine hydrochloride (47.7 g, 0.29 mol), and glacial acetic acid (7.03 g, 6.7 mL, 0.12 mol) were dissolved in abs ethanol (585 mL) and heated under reflux for 18 h. After removal of the solvent under reduced pressure, EtOAc and water (500 mL each) were added, then sodium bicarbonate (42 g, 0.50 mol) was carefully added. After addition of hexane (500 mL), the organic phase was separated, washed with brine (500 mL), and dried over Na2SO4. The mixture was then filtered through a pad of silica gel (500 g) on a sintered glass funnel. The pad was eluted with hexanes/EtOAc (1:1, v/v), and the filtrate was concentrated under reduced pressure. The resulting solid was triturated with hexanes/EtOAc (9:1, v/v), filtered, washed and dried in vacuo to afford a colorless solid (61.5 g, 93%). 1H NMR (400 MHz, CD2Cl2) δ 1.29 (s, 9H), 2.12 (s, 3H), 3.56 (br, 2H), 5.48 (s, 1H), 7.28 (m, 2H), 7.31 (m, 2H).

後処理

  1. temperatureheated
  2. temperatureunder reflux for 18 h
  3. customAfter removal of the solvent under reduced pressure, EtOAc and water (500 mL each)
  4. additionwere added
  5. customthe organic phase was separated
  6. washwashed with brine (500 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationThe mixture was then filtered through a pad of silica gel (500 g) on a sintered glass funnel
  9. washThe pad was eluted with hexanes/EtOAc (1:1
  10. concentrationv/v), and the filtrate was concentrated under reduced pressure
  11. customThe resulting solid was triturated with hexanes/EtOAc (9:1
  12. filtrationv/v), filtered
  13. washwashed
  14. customdried in vacuo

出典と根拠

ORDレコード
ord-eb16afcbaf074028a67597a4ad125252
出典データセット
uspto-grants-2007_09
特許番号
US07265144B2

関連ノート

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