Methyl Acrylate → (E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate

HRID 632684ノート

反応式

HRID 632684 の反応式
Br[C:2]1[CH:19]=[CH:18][C:5]([O:6][C:7]2[C:8]3[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:9]=3[S:10][CH:11]=2)=[CH:4][CH:3]=1.C(N(C(C)C)CC)(C)C.[C:29]([O:33][CH3:34])(=[O:32])[CH:30]=[CH2:31]>CN(C=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>[CH3:17][O:16][C:13]1[CH:14]=[CH:15][C:8]2[C:7]([O:6][C:5]3[CH:18]=[CH:19][C:2](/[CH:31]=[CH:30]/[C:29]([O:33][CH3:34])=[O:32])=[CH:3][CH:4]=3)=[CH:11][S:10][C:9]=2[CH:12]=1

参加物

6

反応物 3

HCID 7294Methyl Acrylate2 回HCID 81531DiisopropylethylamineHCID 867306383-(4-Bromophenoxy)-6-methoxybenzo[b]thiophene

生成物 1

HCID 86730639(E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate収率 64%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
120 °C

実験手順

To a solution of 3-(4-bromophenoxy)-6-methoxybenzo[b]thiophene (125 g, 373 mmol) and Pd(PPh3)2Cl2 (13.09 g, 18.64 mmol) in DMF (2500 mL) and diisopropyl ethylamine (326 mL, 1864 mmol) at room temperature was added (subsurface) methyl acrylate (845 mL, 9322 mmol) over 3-4 hours. As the addition started, the reaction was heated at 120° C. for 13 hours. Methyl acrylate (150 mL, 1654.8 mmol) was added (subsurface). The reaction was heated at 120° C. for 1 hour. The mixture was cooled to RT. Excess methyl acrylate and diisopropyl ethylamine were remove in vacuo. The resulting mixture was filtered through celite pad and the cake was washed with EtOAc (2000 mL). The resulting mixture was washed with water (2×), dried with anhydrous Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatography (SiO2, 5% to 500/(EtOAc/Heptane) to afford (E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate (81 g, 238 mmol, 64% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm=1.46 (s, 3 H), 3.73 (s, 3 H), 6.28 (d, J=16.17 Hz, 1 H), 6.59 (s, 1 H), 6.90 (dd, J=8.59, 2.02 Hz, 1 H), 7.00 (d, J=8.59 Hz, 2 H), 7.21 (d, J=2.02 Hz, 1 H), 7.37-7.48 (m, 3 H), 7.59 (d, J=16.17 Hz, 1 H), LC/MS (m/z. MH+): 341.1.

後処理

  1. additionAs the addition
  2. temperatureThe reaction was heated at 120° C. for 1 hour
  3. temperatureThe mixture was cooled to RT
  4. customExcess methyl acrylate and diisopropyl ethylamine were remove in vacuo
  5. filtrationThe resulting mixture was filtered through celite pad
  6. washthe cake was washed with EtOAc (2000 mL)
  7. washThe resulting mixture was washed with water (2×)
  8. dry with materialdried with anhydrous Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe crude material was purified by column chromatography (SiO2, 5% to 500/(EtOAc/Heptane)

出典と根拠

ORDレコード
ord-6ad2380fe40c411d85f6c3654641de69
出典データセット
uspto-grants-2016_04
特許番号
US09321746B2

反応ノート

読み込み中…