Stannous Chloride → 4,8-Bis(2-ethylhexyl)benzo[1,2-b:4,5-b']dithiophene

HRID 1509353ノート

反応式

HRID 1509353 の反応式
[S:1]1[CH:5]=[CH:4][C:3]2[C:6](=O)[C:7]3[S:8][CH:9]=[CH:10][C:11]=3[C:12](=O)[C:2]1=2.[CH2:15]([CH:17]([CH2:21][CH2:22][CH2:23][CH3:24])[CH2:18][Mg]Br)[CH3:16].Cl[Sn]Cl>C1COCC1.Cl>[CH2:15]([CH:17]([CH2:21][CH2:22][CH2:23][CH3:24])[CH2:18][C:6]1[C:7]2[S:8][CH:9]=[CH:10][C:11]=2[C:12]([CH2:6][CH:3]([CH2:4][CH3:5])[CH2:2][CH2:12][CH2:11][CH3:7])=[C:2]2[S:1][CH:5]=[CH:4][C:3]=12)[CH3:16]

参加物

6

反応物 3

HCID 24479Stannous ChlorideHCID 288478(Benzo(1,2-b:4,5-b)dithiophene-4,8-dione)HCID 178443576HCID 178443576、化合物

生成物 1

HCID 596092024,8-Bis(2-ethylhexyl)benzo[1,2-b:4,5-b']dithiophene収率 13%

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

To a suspension of benzo[1,2-b:4,5-b′]dithiophene-4,8-dione (25) (Beimling, P.; Koβmehl, G. Chem. Ber. 1986, 119, 3198) (4.9 g, 22.2 mmol) in 100 mL of THF was added 2-ethylhexyl magnesium bromide (111 mL, 1M in diethyl ether). The mixture was then heated at 60° C. for 24 h., and cooled to r.t. following by adding SnCl2 (13.47 g, 71.04 mmol) in 190 mL of 10% HCl. The mixture was heated at 60° C. for 24 h. THF was removed under reduced pressure. The residure was dissolved in ether, washed with water, sat. NaHCO3, brine and water. The organic layer was dried over MgSO4 and then concentrated. Column chromatography with hexane gave 1.2 g (13%) of desired product 26. 1H-NMR (400 MHz, CDCl3): ppm 7.46 (d, 2H, J=5.6 Hz), 7.42 (d, 2H, J=5.6 Hz), 3.18-3.06 (m, 4H), 1.97 (hep, 2H, J=6.4 Hz), 1.43-1.18 (m, 16H), 0.91-0.81 (m, 12H).

後処理

  1. temperaturecooled to r.t.
  2. temperatureThe mixture was heated at 60° C. for 24 h
  3. customTHF was removed under reduced pressure
  4. dissolutionThe residure was dissolved in ether
  5. washwashed with water, sat. NaHCO3, brine and water
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-72106297f42a46d294a19713264ac56a
出典データセット
uspto-grants-2015_12
特許番号
US09221944B2

反応ノート

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