Hydrochloric Acid → HCID 69410849、化合物

HRID 1373865ノート

反応式

HRID 1373865 の反応式
[CH2:1]([O:3][C:4](=[O:19])[CH2:5][O:6][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12](Br)[CH:13]=2)[C:8]=1[Br:18])[CH3:2].[S:20]1[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=2[CH:22]=[C:21]1B(O)O.C(=O)([O-])[O-].[K+].[K+].Cl>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:1]([O:3][C:4](=[O:19])[CH2:5][O:6][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:21]3[S:20][C:24]4[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=4[CH:22]=3)[CH:13]=2)[C:8]=1[Br:18])[CH3:2]

参加物

9

反応物 4

HCID 313Hydrochloric AcidHCID 2359Benzo(B)Thiophene-2-Boronic AcidHCID 11430Potassium CarbonateHCID 981253(1,6-Dibromo-naphthalen-2-yloxy)-acetic acid ethyl ester

生成物 1

HCID 69410849HCID 69410849、化合物収率 42%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

A mixture of (1,6-dibromo-naphthalen-2-yloxy)-acetic acid ethyl ester (6.9 g, 18 mmol), benzothiophene-2-boronic acid (4.78 g, 26.8 mmol) in two portions, palladium (II) acetate (0.11 g, 0.49 mmol), potassium carbonate (6.2 g, 45 mmol), tetrabutylammonium bromide (5.8 g, 18 mmol) in water (90 mL) and THF (35 mL) was heated at 70° C. for 3.5 hours. The reaction mixture was allowed to cool to ambient temperature and then poured into excess 2N hydrochloric acid. It was extracted with chloroform. The organic phase was then washed with water and brine. It was dried with anhydrous magnesium sulfate, filtered hot (due to limited solubility) and solvent evaporated. The residue was purified by flash chromatography using 25–45% methylene chloride in hexane and 100% chloroform as eluent. Drying at 60° C. in vacuo for 30 minutes yielded (6-benzo[b]thiophen-2-yl-1-bromo-naphthalen-2-yloxy)-acetic acid ethyl ester as a buff-colored solid (3.3 g, 42%) MP: 178–81° C.; mass spectrum (+EI, M+) m/z 440/442. 1H NMR (500 MHz, DMSO-d6): δ8.32 (d, 1H,J=1.83 Hz), 8.18 (d, 1H, J=8.86 Hz), 8.07–8.12 (m, 2H), 8.01 (d, 2H, J=7.33 Hz), 7.88 (dd, 1H, J=7.63 Hz and 1.07 Hz), 7.47 (d, 1H, J=9.16 Hz), 7.36–7.43 (m, 2H), 5.09 (s, 2H), 4.18 (q, 2H, J=7.08 Hz), 1.22 ppm (t, 3H, J=7.11 Hz). Elemental Analysis for C22H17BrO3S: Calcd: C, 59.87; H, 3.88; N, 0.00; Found: C, 60.03; H, 3.83; N, 0.00.

後処理

  1. temperatureto cool to ambient temperature
  2. extractionIt was extracted with chloroform
  3. washThe organic phase was then washed with water and brine
  4. dry with materialIt was dried with anhydrous magnesium sulfate
  5. filtrationfiltered hot (due to limited solubility) and solvent
  6. customevaporated
  7. customThe residue was purified by flash chromatography
  8. customDrying at 60° C. in vacuo for 30 minutes

出典と根拠

ORDレコード
ord-305b44b5097e4c1890d3e8734962a93a
出典データセット
uspto-grants-2007_01
特許番号
US07163954B2

反応ノート

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