2-Bromo-5-methylthiophene → HCID 59428765、化合物

HRID 504054

反応式

HRID 504054 の反応式
Br[C:2]1[S:3][C:4]([CH3:7])=[CH:5][CH:6]=1.[Mg].[Br:9][C:10]1[CH:14]=[C:13](Br)[S:12][C:11]=1[CH3:16]>CCOCC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Br:9][C:10]1[CH:14]=[C:13]([C:2]2[S:3][C:4]([CH3:7])=[CH:5][CH:6]=2)[S:12][C:11]=1[CH3:16]

参加物

6

反応物 3

HCID 698312-Bromo-5-methylthiopheneHCID 1223733,5-Dibromo-2-methylthiopheneHCID 5462224Magnesium

生成物 1

HCID 59428765HCID 59428765、化合物収率 74%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 3283Diethyl Ether溶媒2 回

実験手順

A solution of 2-bromo-5-methylthiophene (4.00 g, 22.6 mmol) in anhydrous ether (10 mL) was treated with magnesium turnings (0.577 g, 23.7 mmol) and heated at reflux for 45 min under an N2 atmosphere. The heat source was removed and the reaction mixture was slowly allowed to cool to room temperature when it was transferred to a flame-dried addition funnel via a cannula. A solution of 3,5-dibromo-2-methylthiophene (5.49 g, 21.5 mmol) and Pd(dppf)Cl2 (16.5 mg, 0.023 mmol) in 75 mL anhydrous ether was treated dropwise with the solution of the Grignard reagent over 30 min at 0° C. under an N2 atmosphere using an addition funnel. The resulting solution was allowed to slowly warm to room temperature and stirred for 72 h under an N2 atmosphere, when it was quenched with saturated NH4Cl (50 mL). The aqueous layer was separated and extracted with ether (3×75 mL). The combined organic layers were dried over Na2SO4, filtered and evaporated to dryness in vacuo. The crude product was purified by flash chromatography (hexanes) yielding 4.32 g of pure BT3 as a white solid. Yield: 74%.

後処理

  1. temperatureheated
  2. temperatureat reflux for 45 min under an N2 atmosphere
  3. customThe heat source was removed
  4. additionwas transferred to a flame-dried addition funnel via a cannula
  5. temperatureto slowly warm to room temperature
  6. customwhen it was quenched with saturated NH4Cl (50 mL)
  7. customThe aqueous layer was separated
  8. extractionextracted with ether (3×75 mL)
  9. dry with materialThe combined organic layers were dried over Na2SO4
  10. filtrationfiltered
  11. customevaporated to dryness in vacuo
  12. customThe crude product was purified by flash chromatography (hexanes)
  13. customyielding 4.32 g of pure BT3 as a white solid

出典と根拠

ORDレコード
ord-e81adbf25fa44c6ab3e2ecd3d75d9bdb
出典データセット
uspto-grants-2010_08
特許番号
US07777055B2

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