Cyclohexylhydrazine → 6-Bromo-1-cyclohexyl-3-ethyl-1H-indazole

HRID 849314

반응식

HRID 849314 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.[CH:17]1([NH:23][NH2:24])[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1.C([O-])(=O)C.[NH4+]>>[Br:1][C:2]1[CH:7]=[C:6]2[C:5]([C:13]([CH2:14][CH3:15])=[N:24][N:23]2[CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)=[CH:4][CH:3]=1

참가 물질

4

반응물 3

HCID 80993CyclohexylhydrazineHCID 517165Ammonium AcetateHCID 109248095-Bromo-2-propionylphenyl methanesulfonate

생성물 1

HCID 118089646-Bromo-1-cyclohexyl-3-ethyl-1H-indazole수율 76.6%

반응 조건

온도
135 °C

실험 절차

Methanesulfonic acid 5bromo-2-propionyl-phenyl ester (36.6 g, 119 mmol) was combined with cyclohexylhydrazine (27.2 g, 238 mmol) and ammonium acetate (23.0 g, 299 mmol) in xylenes (220 mL). The reaction mixture was heated to 135° C. in a Dean-Stark apparatus for 48 hours. The reaction was cooled to room temperature and concentrated to a low volume under reduced pressure. The crude product was filtered through a pad of silica gel (weight ratio product/silica gel 1/5) eluting first with hexanes then with a 10/90 mixture of ethyl acetate and hexanes. The fractions containing principally 6-bromo-1-cyclohexyl-3-ethyl-1H-indazole were collected. A second crop was obtained by repeating the above silica treatment with the mixed fractions. The two crops were combined and dried under vacuum to yield 28.0 g of 6-bromo-1-cyclohexyl-3-ethyl-1H-indazole (76% yield). 1H NMR (400 MHz, CDCl3) δ 1.35 (t, 3, J=7.7), 1.39-2.06 (m, 10), 2.95 (q, 2, J=7.7), 4.21-4.28(m, 1), 7.15 (d, 1, J=8.5), 7.51 (d, 1, J=8.5), 7.56 (s, 1). 13C NMR (100 MHz, CDCl3) δ 13.95, 20.50, 25.35, 25.84, 32.44, 58.15, 112.01, 120.10, 121.37, 121.65, 122.82, 140.37, 146.60. IR 2934, 2855, 1606, 1502, 1451, 1048, 951, 834 cm-1. Analysis calculated for C15H19BrN2 : C, 58.64; H, 6.23; N, 9.12. Found: C, 58.82; H, 6.20; N, 9.01.

후처리

  1. temperatureThe reaction was cooled to room temperature
  2. concentrationconcentrated to a low volume under reduced pressure
  3. filtrationThe crude product was filtered through a pad of silica gel (weight ratio product/silica gel 1/5)
  4. washeluting first with hexanes
  5. additionwith a 10/90 mixture of ethyl acetate and hexanes
  6. additionThe fractions containing principally 6-bromo-1-cyclohexyl-3-ethyl-1H-indazole
  7. customwere collected
  8. customA second crop was obtained
  9. customdried under vacuum

출처 및 근거

ORD 기록
ord-d4e4cfe2da784731ae1a4a88cb0d7117
출처 데이터셋
uspto-grants-2000_01
특허 번호
US06011159

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