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

HRID 1915811

反応式

HRID 1915811 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%). 1H NMR (400 MHz, CDCl3) δ 8.03 (s, 1H), 5.96-5.86 (m, 2H), 4.13 (s, 3H), 3.70 (s, 1H), 2.63-2.54 (m, 2H), 2.41-2.31 (m, 2H), 2.16-2.03 (m, 2H), 2.00-1.92 (m, 2H).

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-6a49e5f77de74184bfd96bddaf1c40c8
出典データセット
uspto-grants-2013_12
特許番号
US08614206B2

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