Iodine → 3-Iodo-4,5,6,7-tetrahydro-1H-indazole

HRID 246404ノート

反応式

HRID 246404 の反応式
[NH:1]1[C:9]2[CH2:8][CH2:7][CH2:6][CH2:5][C:4]=2[C:3](C(O)=O)=[N:2]1.C(=O)(O)[O-].[Na+].[I-:18].[Na+].II>ClC(Cl)C.O.ClCCl>[I:18][C:3]1[C:4]2[CH2:5][CH2:6][CH2:7][CH2:8][C:9]=2[NH:1][N:2]=1

参加物

8

反応物 4

HCID 807IodineHCID 5238Sodium IodideHCID 516892Sodium BicarbonateHCID 6488524,5,6,7-Tetrahydro-1H-indazole-3-carboxylic acid

生成物 1

HCID 712807353-Iodo-4,5,6,7-tetrahydro-1H-indazole収率 79.3%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 63651,1-Dichloroethane溶媒

反応条件

温度
100 °C

実験手順

To a mixture of 4,5,6,7-tetrahydro-1H-indazole-3-carboxylic acid (0.57 g, 3.43 mmol), and sodium bicarbonate (951 mg, 440 μL, 11.3 mmol) in dichloroethane (5 mL) and water (5 mL) were added in one portion sodium iodide (1.34 g, 8.92 mmol) and iodine (1.13 g, 4.46 mmol) and the mixture heated at to 100° C. (oil bath temperature) with vigorous stirring for 24 h. After cooling to 25° C. the mixture was diluted with dichloromethane, then washed with 10% Na2S2O3 and saturated NaHCO3. The organic phases were combined, dried (MgSO4) and concentrated to an off-white solid which was purified by chromatography (115 g column, 50 μm from Analogix, 0 to 5% over 15 min (MeOH containing 10% ammonium hydroxide)/dichloromethane to give 3-iodo-4,5,6,7-tetrahydro-1H-indazole (674 mg, 2.72 mmol, 79.2%) as a white solid. MS (M+H)+=249 (>90% purity); 1H NMR (CDCl3) δ: 2.75 (t, J=5.7 Hz, 2H), 2.35 (t, J=5.7 Hz, 2H), 1.61-1.90 (m, 4H).

後処理

  1. temperatureAfter cooling to 25° C. the mixture
  2. washwashed with 10% Na2S2O3 and saturated NaHCO3
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated to an off-white solid which
  5. customwas purified by chromatography (115 g column, 50 μm from Analogix, 0 to 5% over 15 min (MeOH containing 10% ammonium hydroxide)/dichloromethane

出典と根拠

ORDレコード
ord-7c9f1b094b114b7496522b6c6007a384
出典データセット
uspto-grants-2014_02
特許番号
US08658646B2

反応ノート

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