Triethylamine → 3-bromo-5-(2,6-difluorophenyl)-2-(2-trimethylsilanylethoxymethyl)-7-trimethylsilanylethynyl-2H-pyrazolo[4,3-c]isoquinoline

HRID 1256228ノート

反応式

HRID 1256228 の反応式
[Br:1][C:2]1[N:3]([CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])[N:4]=[C:5]2[C:14]3[CH:13]=[CH:12][C:11](I)=[CH:10][C:9]=3[C:8]([C:16]3[C:21]([F:22])=[CH:20][CH:19]=[CH:18][C:17]=3[F:23])=[N:7][C:6]=12.C(N([CH2:37][CH3:38])CC)C>CN(C=O)C>[Br:1][C:2]1[N:3]([CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])[N:4]=[C:5]2[C:14]3[CH:13]=[CH:12][C:11]([C:38]#[C:37][Si:28]([CH3:30])([CH3:29])[CH3:27])=[CH:10][C:9]=3[C:8]([C:16]3[C:21]([F:22])=[CH:20][CH:19]=[CH:18][C:17]=3[F:23])=[N:7][C:6]=12

参加物

4

反応物 2

HCID 8471TriethylamineHCID 667704163-bromo-5-(2,6-difluorophenyl)-2-(2-trimethylsilanylethoxymethyl)-7-iodo-2H-pyrazolo[4,3-c]isoquinoline

生成物 1

HCID 667704843-bromo-5-(2,6-difluorophenyl)-2-(2-trimethylsilanylethoxymethyl)-7-trimethylsilanylethynyl-2H-pyrazolo[4,3-c]isoquinoline

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A 10 ml round-bottomed flask equipped with a magnetic stirrer and with a septum having a top-mounted argon intake is charged with 263 mg of 3-bromo-5-(2,6-difluorophenyl)-2-(2-trimethylsilanylethoxymethyl)-7-iodo-2H-pyrazolo[4,3-c]isoquinoline in 1.5 ml of DMF and then 1.5 ml of triethylamine. After argon has been bubbled through the mixture for 10 min, 30 mg of bis(triphenylphosphene)palladium(II) dichloride, 8.7 mg of copper(I) iodide and 118 μl of ethynyltrimethylsilane are added. The mixture is stirred at RT for 2 h, poured into water, extracted with AcOEt, washed with saturated NaCl solution, dried over MgSO4, filtered and concentrated under RP. The product is purified by flash chromatography on silica gel (40-63 μm), eluting with a mixture of DCM and methanol (99.5/0.5 by vol.), to give 140 mg of 3-bromo-5-(2,6-difluorophenyl)-2-(2-trimethylsilanylethoxymethyl)-7-trimethylsilanylethynyl-2H-pyrazolo[4,3-c]isoquinoline (cream solid). MS (E/I): m/z=586 (M+) 1H NMR: −0.05 (s, 9 H) 0.23 (s, 9 H) 0.89 (m, 2 H) 3.72 (m, 2 H) 5.88 (s, 2 H) 7.4 (t, J=8.1 Hz, 2H) 7.6 (broad s, 1H) 7.75 (m, 1H) 8.01 (dd, J=8.3, 1.5 Hz, 1H) 8.52 (d, J=8.3 Hz, 1H).

後処理

  1. customA 10 ml round-bottomed flask equipped with a magnetic stirrer and with a septum
  2. customAfter argon has been bubbled through the mixture for 10 min
  3. addition30 mg of bis(triphenylphosphene)palladium(II) dichloride, 8.7 mg of copper(I) iodide and 118 μl of ethynyltrimethylsilane are added
  4. additionpoured into water
  5. extractionextracted with AcOEt
  6. washwashed with saturated NaCl solution
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under RP
  10. customThe product is purified by flash chromatography on silica gel (40-63 μm)
  11. washeluting with a mixture of DCM and methanol (99.5/0.5 by vol.)

出典と根拠

ORDレコード
ord-f9239cccbc3d4b6da1ca3c2c93fe3bcb
出典データセット
uspto-grants-2013_06
特許番号
US08461175B2

反応ノート

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