Reaktion #469302

Reaktionsgleichung

di-1-adamantylchlorophosphine

ether

magnesium

2-bromo-biphenyl

→

product

Ausbeute 5.8%

2-(di-1-adamantylphosphino)biphenyl

Ausbeute 5.8%

Lösungsmittel

THF

pentane

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeAn oven dried Schlenk tube
2. 2
   SonstigeThe tube was evacuated
3. 3
   workup.ADDITIONTo the above mixture THF (15 mL) was added through a rubber septum
4. 4
   Temperaturthe reaction mixture was heated to
5. 5
   Temperatura mild reflux for 3 hours
6. 6
   TemperaturHeating
7. 7
   Sonstigeformed
8. 8
   FiltrationThe suspension was filtered
9. 9
   Sonstigethe solid was collected on a fritted funnel
10. 10
    SonstigeThe solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 ml, 1:1)
11. 11
    Sonstigeover 30 minutes
12. 12
    WaschenThe aqueos layer washed twice with ether-ethyl acetate (1:1, 100 ml,)
13. 13
    WaschenThe combined organic layers were washed with brine (2×50 mL)
14. 14
    Trocknendried over anhydrous magnesium sulfate
15. 15
    Sonstigedecanted
16. 16
    Einengenconcentrated in vacuo
17. 17
    SonstigeThe product was crystallized from toluene/methanol

Vorschrift

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 addtional 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.

Quelle