Citric Acid → HCID 178497462、化合物

HRID 1861051ノート

反応式

HRID 1861051 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:13]2[CH:21]=[C:20]3[C:16]([CH:17]=[N:18][NH:19]3)=[CH:15][CH:14]=2)[CH:6]=[CH:7][C:8]=1[O:9][CH2:10][O:11][CH3:12].[I:22]I.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.OS([O-])=O.[Na+]>O1CCOCC1.[OH-].[Na+].II.C(OCC)(=O)C.CCCCCC>[I:22][C:17]1[C:16]2[C:20](=[CH:21][C:13]([C:5]3[CH:6]=[CH:7][C:8]([O:9][CH2:10][O:11][CH3:12])=[C:3]([O:2][CH3:1])[CH:4]=3)=[CH:14][CH:15]=2)[NH:19][N:18]=1

参加物

9

反応物 4

HCID 311Citric AcidHCID 807IodineHCID 218774636-(3-methoxy-4-methoxymethoxy-phenyl)-1H-indazoleHCID 23665763Sodium Bisulfite

生成物 1

HCID 178497462HCID 178497462、化合物収率 78%

試薬・触媒・溶媒 4

HCID 807Iodine触媒HCID 14798Sodium Hydroxide溶媒HCID 312751,4-Dioxane溶媒HCID 21226206Ethyl acetate hexane溶媒

実験手順

In a 100-mL round-bottom flask under argon, 6-(3-methoxy-4-methoxymethoxy-phenyl)-1H-indazole (1.19 g, 4.18 mmol, 1 equiv) was dissolved in dioxane (25 mL) and 3N NaOH (14 mL). This mixture was treated with iodine (1.17 g, 14.60 mmol, 1.10 equiv) added in ˜5 portions (˜10 min). Several (˜4) additional portions of iodine (50 mg each) were added until the reaction was complete as visualized by TLC (3:7 ethyl acetate/hexane). The mixture was acidified with 20% citric acid (25 mL) and 5% NaHSO3 (20 mL) was added. The mixture was partitioned between ethyl acetate (150 mL) and water (100 mL). The organic material was washed with saturated sodium bicarbonate (80 mL) and brine (50 mL) and were dried over sodium sulfate and concentrated under reduced pressure. Purification by crystallization from ethyl acetate (3 mL) then hexane (7 mL) gave pure 3-iodo-6-(3-methoxy-4-methoxymethoxy-phenyl)-1H-indazole as a solid (1.33 g, 78%): 1H NMR (CDCl3) δ 10.48 (bs, 1H), 7.62 (s, 1H), 7.57 (d, 1H, J=8.5 Hz), 7.47 (dd, 1H, J=1.3, 8.5 Hz), 7.18 (m, 3H), 5.29 (s, 2H), 3.99 (s, 3H), 3.55 (s, 3H).

後処理

  1. additionadded in ˜5 portions (˜10 min)
  2. additionwas added
  3. customThe mixture was partitioned between ethyl acetate (150 mL) and water (100 mL)
  4. washThe organic material was washed with saturated sodium bicarbonate (80 mL) and brine (50 mL)
  5. dry with materialwere dried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customPurification
  8. customby crystallization from ethyl acetate (3 mL)

出典と根拠

ORDレコード
ord-c0636bc7bb974e96961103b87ca5aa5e
出典データセット
uspto-grants-2003_03
特許番号
US06531491B1

反応ノート

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