Tributylvinyltin → 6-vinyl-1H-indazole

HRID 246035

反応式

HRID 246035 の反応式
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[CH:4][CH:3]=1.[CH2:11]([Sn](CCCC)(CCCC)C=C)[CH2:12]CC>C1(C)C=CC=CC=1.COCCOC.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:11]([C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[CH:4][CH:3]=1)=[CH2:12]

参加物

7

反応物 2

HCID 81998Tributylvinyltin2 回HCID 178424716-Bromo-1H-indazole2 回

生成物 1

HCID 866779366-vinyl-1H-indazole収率 79.6%

試薬・触媒・溶媒 4

HCID 178418476HCID 178418476、化合物触媒2 回HCID 1140Toluene溶媒HCID 80711,2-Dimethoxyethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a suspension of 6-bromo-1H-indazole (600 mg, 3.05 mmol) in toluene (18 ml) and 1,2-dimethoxyethane (6 ml) were added tributyl(vinyl)tin (1.33 ml, 4.57 mmol) and PdCl2(PPh3)2 (214 mg, 0.31 mmol). The reaction was purged with argon then heated at reflux for 3 h. Additional tributyl(vinyl)tin (0.66 ml, 2.28 mmol) and PdCl2(PPh3)2 (107 mg, 0.15 mmol) were added and heating was continued for 1 h. The same reaction was performed on an additional batch of 6-bromo-1H-indazole (200 mg, 1.02 mmol) and the two crude batches were combined. The reactions were diluted with ethyl acetate, washed with water and brine, dried over MgSO4 and concentrated. The residue was purified by silica gel chromatography with 5% to 50% EtOAc/heptane to isolate 350 mg (60%) of 6-vinyl-1H-indazole as a yellow solid. 1H NMR (CDCl3, 300 MHz): δ (ppm) 8.07 (s, 1H), 7.72 (d, J=8.3 Hz, 1H), 7.48 (s, 1H), 7.35 (d, J=8.3 Hz, 1H), 6.85 (dd, J=17.4, 11.0 Hz, 1H), 5.86 (d, J=17.4 Hz, 1H), 5.35 (d, J=11.0 Hz, 1H).

後処理

  1. customThe reaction was purged with argon
  2. temperaturethen heated
  3. temperatureat reflux for 3 h
  4. temperatureheating
  5. customThe same reaction
  6. washwashed with water and brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel chromatography with 5% to 50% EtOAc/heptane

出典と根拠

ORDレコード
ord-8738c4ec8dc447b684710ede3a89b834
出典データセット
uspto-grants-2014_02
特許番号
US08658646B2

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