Hydrazine hydrate (1:1) → 5-Allyl-4-phenyl-3-p-tolyl-1H-pyrazole

HRID 1471932ノート

反応式

HRID 1471932 の反応式
[C:1]1([CH2:7][C:8]([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[N:27]1(C(=O)CC=C)[C:31]2C=C[CH:34]=[CH:35][C:30]=2N=[N:28]1.O.NN>C1COCC1.CCO>[CH2:30]([C:31]1[NH:27][N:28]=[C:8]([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)[C:7]=1[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH:35]=[CH2:34]

参加物

7

反応物 4

HCID 24654Hydrazine hydrate (1:1)HCID 2280161-(4-Methylphenyl)-2-phenylethan-1-oneHCID 2733832Lithium HexamethyldisilazideHCID 673843391-(1H-Benzo[d][1,2,3]triazol-1-yl)but-3-en-1-one

生成物 1

HCID 673845665-Allyl-4-phenyl-3-p-tolyl-1H-pyrazole収率 36%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 2-phenyl-1-p-tolylethanone (1.0 g, 4.76 mmol) in THF (10 mL) added LiHMDS (1.0 M in THF) (9.51 mL, 9.51 mmol) slowly via syringe at 0° C. After stirring for 10 min, 1-(1H-benzo[d][1,2,3]triazol-1-yl)but-3-en-1-one (1.068 g, 5.71 mmol) was added in one portion. The reaction was stirred at 0° C. for 30 min and then quenched with AcOH (2 mL). EtOH (30 mL) and hydrazine hydrate (0.714 g, 14.27 mmol) were added, and the reaction was heated to reflux for 30 min. The reaction was cooled to room temperature, concentrated and the residue was extracted with EtOAc/H2O, washed with brine, dried over MgSO4, and purified by column chromatography to give the title compound as clear oil (0.47 g). LCMS m/z=275.0 [M+H]+; 1H NMR (400 MHz, CDCl3) δ ppm 2.31 (s, 3H), 3.38-3.43 (m, 2H), 5.07-5.14 (m, 2H), 5.90-6.01 (m, 1H), 7.03-7.09 (m, 2H), 7.19-7.30 (m, 5H), 7.30-7.36 (m, 2H).

後処理

  1. stirringThe reaction was stirred at 0° C. for 30 min
  2. customquenched with AcOH (2 mL)
  3. temperaturethe reaction was heated
  4. temperatureto reflux for 30 min
  5. concentrationconcentrated
  6. extractionthe residue was extracted with EtOAc/H2O
  7. washwashed with brine
  8. dry with materialdried over MgSO4
  9. custompurified by column chromatography

出典と根拠

ORDレコード
ord-84b0128d56e044d48283952a1b60458f
出典データセット
uspto-grants-2015_04
特許番号
US09012478B2

反応ノート

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