Diisopropylamine → N,N-Dimethyl-2-(4-((trimethylsilyl)ethynyl)-1H-pyrazol-1-yl)acetamide

HRID 2205910ノート

反応式

HRID 2205910 の反応式
I[C:2]1[CH:3]=[N:4][N:5]([CH2:7][C:8]([N:10]([CH3:12])[CH3:11])=[O:9])[CH:6]=1.[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15].C(NC(C)C)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.[Cu]I.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:11][N:10]([CH3:12])[C:8](=[O:9])[CH2:7][N:5]1[CH:6]=[C:2]([C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13])[CH:3]=[N:4]1

参加物

8

反応物 4

HCID 7912DiisopropylamineHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 644307842-(4-Iodo-1H-pyrazol-1-yl)-N,N-dimethylacetamide

生成物 1

HCID 68290932N,N-Dimethyl-2-(4-((trimethylsilyl)ethynyl)-1H-pyrazol-1-yl)acetamide収率 91.1%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
60 °C

実験手順

2-(4-Iodo-1H-pyrazol-1-yl)-N,N-dimethylacetamide (Preparation 99, 0.68 g, 2.42 mmol) and trimethylsilylacetylene (0.326 g, 3.32 mmol) were dissolved in dry DMF (5 ml) and placed under argon. Diisopropylamine (0.47 ml, 3.3 mmol), copper (1) iodide (30 mg, 0.16 mmol), triphenylphosphine (126 mg, 0.242 mmol) and palladium acetate (40 mg, 0.16 mmol) were added and the flask was flushed with argon. The reaction was heated to 60° C. for 1 hour. The reaction was cooled to room temperature and diluted with ethyl acetate (30 ml). The organic solution was washed with water, brine, dried over sodium sulphate and filtered. The solvent was removed in vacuum and the crude purified on silica gel column chromatography eluting with neat ethyl acetate to afford the title compound as a pale yellow powder (0.55 g, 91%). 1H-NMR (500 MHz, CDCl3): δ 0.21 (s, 9H), 2.96 (s, 3H), 3.04 (s, 3H), 4.92 (s, 2H), 7.59 (s, 1H), 7.65 (s, 1H).

後処理

  1. customthe flask was flushed with argon
  2. temperatureThe reaction was cooled to room temperature
  3. additiondiluted with ethyl acetate (30 ml)
  4. washThe organic solution was washed with water, brine
  5. dry with materialdried over sodium sulphate
  6. filtrationfiltered
  7. customThe solvent was removed in vacuum
  8. customthe crude purified on silica gel column chromatography
  9. washeluting with neat ethyl acetate

出典と根拠

ORDレコード
ord-c722d32839834f05a776eb7ceeaadf44
出典データセット
uspto-grants-2016_06
特許番号
US09371319B2

反応ノート

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