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

HRID 849314

反応式

HRID 849314 の反応式
[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

参加物

4

反応物 3

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

生成物 1

HCID 118089646-Bromo-1-cyclohexyl-3-ethyl-1H-indazole収率 76.6%

反応条件

温度
135 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-d4e4cfe2da784731ae1a4a88cb0d7117
出典データセット
uspto-grants-2000_01
特許番号
US06011159

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