تفاعل #315067

معادلة التفاعل

di-1-adamantylchlorophosphine

ether

magnesium

2-bromo-biphenyl

→

product

المردود 5.8%

2-(di-1-adamantylphosphino)biphenyl

المردود 5.8%

المذيبات

THF

pentane

ظروف التفاعل

المعالجة

1. 1
   أخرىAn oven dried Schlenk tube
2. 2
   أخرىThe tube was evacuated
3. 3
   workup.ADDITIONTo the above mixture THF (15 mL) was added through a rubber septum
4. 4
   درجة الحرارةthe reaction mixture was heated to
5. 5
   درجة الحرارةa mild reflux for 3 hours
6. 6
   درجة الحرارةHeating
7. 7
   أخرىformed
8. 8
   ترشيحThe suspension was filtered
9. 9
   أخرىthe solid was collected on a fritted funnel
10. 10
    أخرىThe solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1)
11. 11
    أخرىover 30 minutes
12. 12
    غسيلThe aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL)
13. 13
    غسيلThe combined organic layers were washed with brine (2×50 mL)
14. 14
    تجفيفdried over anhydrous magnesium sulfate
15. 15
    أخرىdecanted
16. 16
    تركيزconcentrated in vacuo
17. 17
    أخرىThe product was crystallized from toluene/methanol

الإجراء التجريبي

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.

المصدر