Diethyl Ether → 2-[Bis(1-adamantyl)phosphino]biphenyl

HRID 227885

반응식

HRID 227885 반응식
[Mg].Br[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[C:15]12([P:25]([C:27]34[CH2:36][CH:31]5[CH2:32][CH:33]([CH2:35][CH:29]([CH2:30]5)[CH2:28]3)[CH2:34]4)Cl)[CH2:24][CH:19]3[CH2:20][CH:21]([CH2:23][CH:17]([CH2:18]3)[CH2:16]1)[CH2:22]2.CCOCC>C1COCC1.CCCCC>[C:15]12([P:25]([C:27]34[CH2:28][CH:29]5[CH2:30][CH:31]([CH2:32][CH:33]([CH2:35]5)[CH2:34]3)[CH2:36]4)[C:3]3[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=3[C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=3)[CH2:16][CH:17]3[CH2:23][CH:21]([CH2:20][CH:19]([CH2:18]3)[CH2:24]1)[CH2:22]2

참가 물질

7

반응물 4

HCID 3283Diethyl EtherHCID 163292-BromobiphenylHCID 5462224MagnesiumHCID 11110495Di-1-adamantylchlorophosphine

생성물 1

HCID 98685882-[Bis(1-adamantyl)phosphino]biphenyl수율 5.8%

시약·촉매·용매 2

HCID 8003Pentane용매HCID 8028Tetrahydrofuran용매

실험 절차

An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-1-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an additional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 mL) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid.

후처리

  1. customAn oven dried Schlenk tube
  2. customThe tube was evacuated
  3. additionTo the above mixture THF (15 mL) was added through a rubber septum
  4. temperaturethe reaction mixture was heated to
  5. temperaturea mild reflux for 3 hours
  6. temperatureHeating
  7. customformed
  8. filtrationThe suspension was filtered
  9. customthe solid was collected on a fritted funnel
  10. customThe solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1)
  11. customover 30 minutes
  12. washThe aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL)
  13. washThe combined organic layers were washed with brine (2×50 mL)
  14. dry with materialdried over anhydrous magnesium sulfate
  15. customdecanted
  16. concentrationconcentrated in vacuo
  17. customThe product was crystallized from toluene/methanol

출처 및 근거

ORD 기록
ord-a5ec27e2f28944c39f78650ee09f0dae
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560582B2

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