Methylhydrazine → 6-Bromo-3-ethyl-1-methylindazole

HRID 849315노트

반응식

HRID 849315 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.[CH3:17][NH:18][NH2:19].C([O-])(=O)C.[NH4+]>ClCCl>[Br:1][C:2]1[CH:7]=[C:6]2[C:5]([C:13]([CH2:14][CH3:15])=[N:19][N:18]2[CH3:17])=[CH:4][CH:3]=1

참가 물질

5

반응물 3

HCID 6061MethylhydrazineHCID 517165Ammonium AcetateHCID 109248095-Bromo-2-propionylphenyl methanesulfonate

생성물 1

HCID 154392626-Bromo-3-ethyl-1-methylindazole수율 77.1%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
135 °C

실험 절차

Methanesulfonic acid 5-bromo-2-propionyl-phenyl ester (2.00 g, 6.51 mmol) was combined with methylhydrazine (0.69 mL, 13 mmol) and ammonium acetate (1.30 g, 16.9 mmol) in xylenes (12 mL). The reaction mixture was heated to 135° C. for 18 hours using a Dean Stark apparatus. The reaction was cooled to room temperature, diluted with dichloromethane (50 mL), and washed with water (50 mL) and 1N aqueous hydrochloric acid (50 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 1.20 g of 6-bromo-1-methyl-3ethyl-1H-indazole (75% yield). 1H NMR (400 MHz, CDCl3) δ 1.35 (t, 3, J=7.7), 2.94 (q, 2, J=7.7), 3.95 (s, 3), 7.18 (dd, 1, J=8.5, 1.5), 7.50 (d, J=0.8), 7.52 (dd, 1, J=8.5, 0.6). 13C NMR (100 MHz, CDCl3) δ 13.66, 20.29, 35.21, 111.82, 120.61, 121.35, 121.60, 123.05, 141.68, 147.08. IR 2970, 2935, 1609, 1506, 1458, 1223, 1047, 819, 805 cm-1. Analysis calculated for C10H11BrN2 : C, 50.23; H, 4.64; N, 11.72. Found: C, 50.14; H, 4.57; N, 11.46.

후처리

  1. temperatureThe reaction was cooled to room temperature
  2. washwashed with water (50 mL) and 1N aqueous hydrochloric acid (50 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-c13183bd6541483082acabe1ee044b9d
출처 데이터셋
uspto-grants-2000_01
특허 번호
US06011159

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