Benzylhydrazine dihydrochloride → 1-benzyl-6-bromo-3-ethyl-1H-indazole

HRID 849316노트

반응식

HRID 849316 반응식
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:13](=O)[CH2:14][CH3:15])=[C:6](OS(C)(=O)=O)[CH:7]=1.Cl.Cl.[CH2:19]([NH:26][NH2:27])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C([O-])(=O)C.[Na+]>ClCCl>[Br:1][C:2]1[CH:7]=[C:6]2[C:5]([C:13]([CH2:14][CH3:15])=[N:27][N:26]2[CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:4][CH:3]=1

참가 물질

5

반응물 3

HCID 146540Benzylhydrazine dihydrochlorideHCID 517045Sodium AcetateHCID 109248095-Bromo-2-propionylphenyl methanesulfonate

생성물 1

HCID 154293321-benzyl-6-bromo-3-ethyl-1H-indazole수율 41%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
135 °C

실험 절차

Methanesulfonic acid 5-bromo-2-propionyl-phenyl ester (5.00 g, 16.3 mmol) was combined with benzylhydrazine dihydrochloride (4.45 g, 22.8 mmol) and sodium acetate (4.01 g, 48.9 mmol) in xylenes (30 mL). The reaction mixture was heated to 135° C. for two days using a Dean Stark apparatus. The reaction was cooled to room temperature, diluted with dichloromethane (75 mL), and washed with water (75 mL) and 1N aqueous hydrochloric acid (75 mL). The organic extracts were dried over magnesium sulfate and concentrated. The crude product was purified by chromatography on silica gel eluting with 4:1 hexanes/ethyl acetate to yield 2.10 g of 6-bromo-1-benzyl-3ethyl-1H-indazole (41% yield). 1H NMR (400 MHz, CDCl3) δ 1.39 (t, 3, J=7.7), 2.96 (q, 2, J=7.7), 5.48 (s, 2), 7.14-7.23 (m, 3), 7.26-7.31 (m, 3), 7.42 (s, 1), 7.54 (d, 1, J=8.5). 13C NMR (100 MHz, CDCl3) δ 13.70, 20.37, 52.68, 112.12, 120.77, 121.69, 121.83, 123.34, 126.97, 127.76, 128.75, 136.74, 141.37, 147.60. IR 3064, 3031, 2970, 2934, 2875, 1606, 1504, 1497, 1454, 1236, 1048, 831, 701 cm1. Analysis calculated for C16H15BrN2 : C, 60.97; H, 4.80; N, 8.89. Found: C, 61.21; H, 4.92; N, 8.73.

후처리

  1. temperatureThe reaction was cooled to room temperature
  2. washwashed with water (75 mL) and 1N aqueous hydrochloric acid (75 mL)
  3. dry with materialThe organic extracts were dried over magnesium sulfate
  4. concentrationconcentrated
  5. customThe crude product was purified by chromatography on silica gel eluting with 4:1 hexanes/ethyl acetate

출처 및 근거

ORD 기록
ord-8d1cc5c679d14e098b43a6296952c9a2
출처 데이터셋
uspto-grants-2000_01
특허 번호
US06011159

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