تفاعل #469301

معادلة التفاعل

magnesium

1-bromoadamantane

PCl3

→

di-1-adamantylchlorophosphine

المذيبات

ether

ظروف التفاعل

المعالجة

1. 1
   أخرىThe flask was evacuated
2. 2
   workup.ADDITIONTo the reaction vessel 45 mL ether was added
3. 3
   درجة الحرارةthe mixture was gently refluxed for 15 hours, without mechanical stirring
4. 4
   أخرىThe resulting solution of Grignard reagent was taken up in a syringe
5. 5
   workup.ADDITIONadded very slowly dropwise to a separate
6. 6
   أخرىflame-dried
7. 7
   أخرىtwo-necked, round-bottom flask equipped with a reflux condenser which
8. 8
   أخرىhad been coooled to −40° C
9. 9
   workup.ADDITIONDuring the addition the temperature
10. 10
    أخرىkept below −25° C
11. 11
    أخرىthe cooling bath was removed
12. 12
    درجة الحرارةto warm slowly to room temperature
13. 13
    workup.STIRRINGAfter stirring for an additional 30 minutes at room temperature
14. 14
    أخرىwas placed into a heated oilbath (37° C.)
15. 15
    درجة الحرارةwas gently refluxed for 22 hours
16. 16
    درجة الحرارةThe mixture was cooled to room temperature
17. 17
    ترشيحthe solution was filtered through a cannula
18. 18
    ترشيحfilter
19. 19
    أخرىThe solvent as well as some of the adamantane byproduct was removed in vacuo

الإجراء التجريبي

An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been coooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oilbath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine.

المصدر