Stannous Chloride → HCID 59609198、化合物

HRID 405039

反応式

HRID 405039 の反応式
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[CH:13]([Mg]Cl)([CH3:15])[CH3:14].[S:18]1[CH:22]=[CH:21][C:20]2[C:23](=O)[C:24]3[S:25][CH:26]=[CH:27][C:28]=3[C:29](=O)[C:19]1=2.Cl[Sn]Cl>C1COCC1.Cl.[Cl-].[Na+].O>[C:1]([C:23]1[C:24]2[S:25][CH:26]=[CH:27][C:28]=2[C:29]([C:14]#[C:13][CH2:15][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])=[C:19]2[S:18][CH:22]=[CH:21][C:20]=12)#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

参加物

8

反応物 4

HCID 24479Stannous ChlorideHCID 698211-DodecyneHCID 288478(Benzo(1,2-b:4,5-b)dithiophene-4,8-dione)HCID 178418918HCID 178418918、化合物

生成物 1

HCID 59609198HCID 59609198、化合物収率 57%

試薬・触媒・溶媒 3

HCID 313Hydrochloric Acid溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 57417360Sodium chloride; water溶媒

反応条件

温度
50 °C

実験手順

To a solution of dodecyne (17.5 mL, 81.7 mmol) in THF (20 mL) in a 250 mL flask equipped with a condenser under an argon atmosphere was added dropwise 36 mL (72 mmol) of a 2 M solution of isopropylmagnesium chloride in THF at room temperature. After addition, the reaction mixture was heated at 50° C. for 95 min and cooled to room temperature. 4,8-Dihydrobenzo[1,2-b:4,5-b′]dithiophene-4,8-dione (3 g, 13.6 mmol) was added, and the mixture was heated at 50° C. for 1 hour before cooling down to room temperature. Subsequently, a solution of 20 g of SnCl2 in 50 mL 10% aqueous HCl solution was added in a dropwise fashion followed by further heating at 60° C. for 1 hour. After the reaction, brine (30 mL) was added. The organic phase was separated and evaporated under vacuum. The residue was diluted with MeOH (100 mL) and filtered. The solid was washed with MeOH several times. The brown solid was purified by column chromatography with CHCl3:hexane 5:6 as eluent. Recrystallization of the crude product collected from flash chromatography from hexane gave 4.03 g (57% yield) of a pale yellow crystal after drying in vacuo. 1H NMR (CDCl3, 500 MHz), δ=7.59 (d, J=5.5 Hz, 2H), 7.51 (d, J=6.0 Hz, 2H), 2.65 (t, J=6.5 Hz, 4H), 1.70-1.80 (m, 4H), 1.56-1.65 (m, 4H), 1.22-1.47 (m, 24H), 0.90 (t, J=6.5 Hz, 6H).

後処理

  1. additionAfter addition
  2. temperaturecooled to room temperature
  3. temperaturethe mixture was heated at 50° C. for 1 hour
  4. temperaturebefore cooling down to room temperature
  5. temperatureby further heating at 60° C. for 1 hour
  6. additionwas added
  7. customThe organic phase was separated
  8. customevaporated under vacuum
  9. additionThe residue was diluted with MeOH (100 mL)
  10. filtrationfiltered
  11. washThe solid was washed with MeOH several times
  12. customThe brown solid was purified by column chromatography with CHCl3:hexane 5:6 as eluent
  13. customRecrystallization of the crude product
  14. customcollected from flash chromatography from hexane

出典と根拠

ORDレコード
ord-dcbce6d826744041abdb4d2490cf7f51
出典データセット
uspto-grants-2014_06
特許番号
US08748739B2

関連ノート

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