1-methyl-4-nitro-1H-pyrazole → (Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol

HRID 521942

反応式

HRID 521942 の反応式
[CH3:1][N:2]1[CH:6]=[C:5]([N+:7]([O-:9])=[O:8])[CH:4]=[N:3]1.[C:10]1(=[O:17])[CH2:16][CH2:15][CH:14]=[CH:13][CH2:12][CH2:11]1.C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[Cl-].[NH4+]>C1COCC1>[CH3:1][N:2]1[C:6]([C:10]2([OH:17])[CH2:16][CH2:15][CH:14]=[CH:13][CH2:12][CH2:11]2)=[C:5]([N+:7]([O-:9])=[O:8])[CH:4]=[N:3]1

参加物

6

反応物 4

HCID 198951-methyl-4-nitro-1H-pyrazoleHCID 25517Ammonium ChlorideHCID 549335Cyclohept-4-en-1-oneHCID 2733832Lithium Hexamethyldisilazide

生成物 1

HCID 86680017(Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol収率 49%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-40 °C

実験手順

To a solution of 1-methyl-4-nitro-1H-pyrazole (1.5 g, 11.8 mmol) and (Z)-cyclohept-4-enone (1.4 g, 13.0 mmol) in dry THF (30 mL) under nitrogen cooled to −78° C. was added dropwise a solution of lithium hexamethyldisilazide (1.0 M in THF, 30 mL, 29.5 mmol). The reaction mixture was allowed to warm to −40° C. and stirred for 90 min. Saturated aqueous ammonium chloride solution (30 mL) was added (dropwise initially) and the mixture was allowed to warm to room temperature and extracted with EtOAc (150 mL). The organic layer was washed with water (30 mL), washed with brine (20 mL), separated, dried over MgSO4 and concentrated under reduced pressure. Purification via silica gel column chromatography (20-25% EtOAc) gave (Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol as a tan oil (1.37 g, 49%).

後処理

  1. temperatureto warm to room temperature
  2. extractionextracted with EtOAc (150 mL)
  3. washThe organic layer was washed with water (30 mL)
  4. washwashed with brine (20 mL)
  5. customseparated
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated under reduced pressure
  8. customPurification via silica gel column chromatography (20-25% EtOAc)

出典と根拠

ORDレコード
ord-2fc1cce7738e49f3a797f537f2d6e4e8
出典データセット
uspto-grants-2016_05
特許番号
US09328106B2

関連ノート

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