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

HRID 1471932노트

반응식

HRID 1471932 반응식
[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]

참가 물질

7

반응물 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

생성물 1

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

시약·촉매·용매 2

HCID 702Ethanol용매HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-84b0128d56e044d48283952a1b60458f
출처 데이터셋
uspto-grants-2015_04
특허 번호
US09012478B2

반응 노트

불러오는 중…