Reaktion #469301

Reaktionsgleichung

magnesium

1-bromoadamantane

PCl3

→

di-1-adamantylchlorophosphine

Lösungsmittel

ether

Reaktionsbedingungen

Aufarbeitung

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

Vorschrift

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.

Quelle