Iodine → 2-(Di-tert-butylphosphino)biphenyl

HRID 227863

반응식

HRID 227863 반응식
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.II.[Mg].Cl[P:18]([C:23]([CH3:26])([CH3:25])[CH3:24])[C:19]([CH3:22])([CH3:21])[CH3:20]>C1COCC1>[C:19]([P:18]([C:23]([CH3:26])([CH3:25])[CH3:24])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([CH3:22])([CH3:21])[CH3:20]

참가 물질

6

반응물 4

HCID 807IodineHCID 163292-BromobiphenylHCID 139566Di-tert-butylchlorophosphineHCID 5462224Magnesium

생성물 1

HCID 27342152-(Di-tert-butylphosphino)biphenyl수율 58%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

A solution of 2-bromobiphenyl (5.38 g, 23.1 mmol) and a few iodine crystals in 40 mL of THF with magnesium turnings (617 mg, 25.4 mmol) was heated to a reflux for 2 h. Heat was temporarily removed for the addition of cuprous chloride (2.40 g, 24.2 mmol) followed by chlorodi-tert-butylphosphine. Heating was resumed for 8 h. The reaction mixture was then removed from heat and allowed to cool to rt. The reaction mixture was poured onto 200 mL of 1:1 hexane/ether. The suspension was filtered and the filtercake was washed with 60 mL of hexane. The solid was partitioned between 150 mL of 1:1 hexane/ethyl acetate and 60 mL of concentrated ammonium hydroxide with 100 mL of water. The organic layer was washed with 100 mL of brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The white solid was recrystallized from 30 mL of MeOH to give white crystals of 2-(di-tert-butylphosphino)biphenyl (4.01 g, 58%). A second crop (464 mg, 67%) was obtained by recrystallization from 50 mL of MeOH and 25 mL of water.

후처리

  1. temperaturea reflux for 2 h
  2. temperatureHeat
  3. temperatureHeating
  4. customThe reaction mixture was then removed
  5. temperaturefrom heat
  6. additionThe reaction mixture was poured onto 200 mL of 1:1 hexane/ether
  7. filtrationThe suspension was filtered
  8. washthe filtercake was washed with 60 mL of hexane
  9. customThe solid was partitioned between 150 mL of 1:1 hexane/ethyl acetate and 60 mL of concentrated ammonium hydroxide with 100 mL of water
  10. washThe organic layer was washed with 100 mL of brine
  11. dry with materialdried over anhydrous sodium sulfate
  12. concentrationconcentrated in vacuo
  13. customThe white solid was recrystallized from 30 mL of MeOH

출처 및 근거

ORD 기록
ord-98120683f6664ec1ac6c9d02de2e9e8f
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560582B2

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