反応 #2507816

反応方程式

dimethyladamantyl bromide

1,1,1,4,4-pentachloro-1,4-disilabutane

allylbromide

3,5-dimethyladamantylbromide

→

1,1,1,4,4-Pentachloro-7-(3,5-dimethyladamantyl)-1,4-disilaheptane

溶媒

pentane

反応条件

後処理

1. 1
   温度The solution was cooled to below −10° C. by ice/acetone bath
2. 2
   その他10° C.
3. 3
   workup.STIRRINGsolution was stirred for an additional two hours after which GC-MS
4. 4
   その他had reacted
5. 5
   洗浄it was washed twice with 500 ml water
6. 6
   その他The organic layer was collected
7. 7
   その他pentane was evaporated
8. 8
   workup.DISSOLUTIONRemaining material was dissolved to 700 ml ethanol
9. 9
   workup.ADDITIONa small amount of water was added
10. 10
    温度The solution was then heated up
11. 11
    温度to reflux
12. 12
    workup.STIRRINGit was stirred for 15 h
13. 13
    温度After cooling down to room temperature the solution
14. 14
    ろ過was filtered
15. 15
    workup.ADDITION300 ml water was added
16. 16
    抽出the product was extracted
17. 17
    洗浄by washing twice with 500 ml pentane
18. 18
    その他Pentane layers were collected
19. 19
    洗浄washed once with water
20. 20
    その他The organic layer were collected
21. 21
    乾燥dried with anhydrous magnesium sulfate
22. 22
    ろ過filtered
23. 23
    その他Pentane was evaporated
24. 24
    workup.DISTILLATIONwas purified by distillation, yield 45.90 g (67%)
25. 25
    その他1-allyl-3,5-dimethyladamantane was moved to a 100 ml vessel
26. 26
    温度The solution was heated up to 85° C.
27. 27
    workup.ADDITIONAfter addition
28. 28
    温度the solution was heated up to 100° C.
29. 29
    workup.STIRRINGit was stirred for an hour
30. 30
    その他The product thus obtained
31. 31
    workup.DISTILLATIONwas then purified by distillation
32. 32
    その他yielding 53.54 g (51%), bp. 157-158° C./<0.5 mbar

実験手順

81.71 g (0.336 mol) 3,5-dimethyladamantylbromide was dissolved in 500 ml pentane. The solution was cooled to below −10° C. by ice/acetone bath. 51.40 g (0.425 mol) allylbromide was added followed by 410 mg FeBr3. The solution was then stirred for three hours at −20 . . . 10° C. after which analysis by GC-MS was carried out, indicating that some unreacted starting materials remained. 420 mg FeBr3 was added and solution was stirred for an additional two hours after which GC-MS showed that all the dimethyladamantyl bromide had reacted. The solution was warmed up to room temperature and it was washed twice with 500 ml water. The organic layer was collected and pentane was evaporated. Remaining material was dissolved to 700 ml ethanol and a small amount of water was added followed by 25 g (0.382 mol) metallic zinc. The solution was then heated up to reflux and it was stirred for 15 h. After cooling down to room temperature the solution was filtered. 300 ml water was added and the product was extracted by washing twice with 500 ml pentane. Pentane layers were collected and washed once with water. The organic layer were collected, dried with anhydrous magnesium sulfate and filtered. Pentane was evaporated and remaining crude 1-allyl-3,5-dimethyladamantane was purified by distillation, yield 45.90 g (67%). 1-allyl-3,5-dimethyladamantane was moved to a 100 ml vessel followed by 50 μl H2PtCl6/IPA solution. The solution was heated up to 85° C. and 59.50 g (0.227 mol) 1,1,1,4,4-pentachloro-1,4-disilabutane was added slowly during 30 min. After addition, the solution was heated up to 100° C. and it was stirred for an hour. The product thus obtained was then purified by distillation yielding 53.54 g (51%), bp. 157-158° C./<0.5 mbar.

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