Triethylamine → 5-Nitro-3-(trimethylsilylethynyl)-indazole-1 carboxylic acid tert-butyl ester

HRID 1823916ノート

反応式

HRID 1823916 の反応式
[C:1]([O:5][C:6]([N:8]1[C:16]2[C:11](=[CH:12][C:13]([N+:17]([O-:19])=[O:18])=[CH:14][CH:15]=2)[C:10](Br)=[N:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.[CH3:28][Si:29]([C:32]#[CH:33])([CH3:31])[CH3:30]>CN(C=O)C.[Cu](I)I>[C:1]([O:5][C:6]([N:8]1[C:16]2[C:11](=[CH:12][C:13]([N+:17]([O-:19])=[O:18])=[CH:14][CH:15]=2)[C:10]([C:33]#[C:32][Si:29]([CH3:31])([CH3:30])[CH3:28])=[N:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

6

反応物 3

HCID 8471Triethylamine2 回HCID 66111TrimethylsilylacetyleneHCID 222608361-Boc-3-bromo-5-nitro-1H-indazole

生成物 1

HCID 600647035-Nitro-3-(trimethylsilylethynyl)-indazole-1 carboxylic acid tert-butyl ester収率 45.1%

試薬・触媒・溶媒 2

HCID 83717Copper iodide触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
50 °C

実験手順

3-Bromo 5-nitro-indazole-1-carboxylic acid tert-butyl ester (2 g, 5.8 mmol) was dissolved in dry DMF (30 mL) under nitrogen and triethylamine (1.6 mL, 1.6 mmol) added. Copper iodide (20 mg, 0.12 mmol), trimethylsilylacetylene (2.5 mL, 17.4 mmol) palladium bis-triphenylphosphine dichloride (84 mg, 0.12 mmol) and a further 1.6 mL of triethylamine were added and the mixture heated at 50° C. overnight. The reaction mixture was allowed to cool to room temperature and concentrated. The residue was taken up in EtOAc and filtered through a plug of Celite®. The filtrate was washed with saturated ammonium chloride solution and dried over sodium sulfate then concentrated to a black foam. Purification by chromatography (silica, 1:1 petrol-EtOAc) gave the title compound as a black solid (940 mg, 45%); MS (ES+) m/e=360.

後処理

  1. temperatureto cool to room temperature
  2. concentrationconcentrated
  3. filtrationfiltered through a plug of Celite®
  4. washThe filtrate was washed with saturated ammonium chloride solution
  5. dry with materialdried over sodium sulfate
  6. concentrationthen concentrated to a black foam
  7. customPurification by chromatography (silica, 1:1 petrol-EtOAc)

出典と根拠

ORDレコード
ord-55b7a0b7624949af99d16aead348262a
出典データセット
uspto-grants-2006_05
特許番号
US07041687B2

反応ノート

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