Reaktion #1058352

Reaktionsgleichung

n-BuLi n-hexane

adamantanone

2-cyanomethyl-2-adamantanol

Acetonitrile

adamantanone

methacrylic anhydride

triethylamine

→

2-cyanomethyl-2-adamantyl Methacrylate

Lösungsmittel

diethyl ether

water

tetrahydrofuran

water

tetrahydrofuran

tetrahydrofuran

n-Hexane

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeA glass reactor of 500 ml which was equipped with a stirrer
2. 2
   SonstigeA solution obtained
3. 3
   workup.ADDITIONwas dropwise added
4. 4
   workup.DISSOLUTIONThe deposit was slowly dissolved
5. 5
   workup.ADDITIONAfter finishing dropwise adding
6. 6
   Sonstigewas slowly elevated up to 0° C.
7. 7
   SonstigeThis reaction liquid
8. 8
   workup.STIRRINGstirred
9. 9
   SonstigeThis solution was transferred into a separating funnel of 2 liter
10. 10
    Sonstigeto remove an aqueous phase
11. 11
    Waschenan organic phase was washed with diluted hydrochloric acid
12. 12
    Sonstigeto remove a Li salt
13. 13
    Waschenwashed with water
14. 14
    TrocknenThe organic phase was dried on anhydrous magnesium sulfate
15. 15
    workup.DISTILLATIONthe solvent was distilled off by means of an evaporator
16. 16
    Sonstigeto obtain 38 g of a crude
17. 17
    Sonstigereaction product
18. 18
    Sonstigereaction product
19. 19
    Temperaturthe solution was cooled
20. 20
    workup.STIRRINGwhile stirring
21. 21
    Sonstigeto remove
22. 22
    Filtrationby filtration
23. 23
    workup.ADDITIONActivated carbon was added to the n-hexane solution
24. 24
    Filtrationit was filtered off
25. 25
    workup.DISTILLATIONThen, the solvent was distilled off by means of an evaporator
26. 26
    Sonstigeto obtain a colorless liquid
27. 27
    Sonstigewas obtained at a yield of 35.0 g

Vorschrift

A glass reactor of 500 ml which was equipped with a stirrer and dropping funnel was charged with 100 ml of dried tetrahydrofuran, and it was cooled (−78° C.) on a dry ice/isopropanol bath and then charged with 100 ml (160 millimole) of a n-BuLi/n-hexane solution (1.6M). Acetonitrile 10 ml (192 millimole) was dropwise added thereto in 10 minutes. The solution stayed in a slurry state by a deposit. A solution obtained by dissolving 22.2 g (148 millimole) of adamantanone (Adamantanone, manufactured by Idemitsu Petrochemical Co., Ltd.) in 100 ml of tetrahydrofuran was dropwise added thereto. The deposit was slowly dissolved, and the solution became transparent. After finishing dropwise adding, the temperature was slowly elevated up to 0° C., and gas chromatographic analysis was carried out to confirm that adamantanone was completely converted to Li alkoxide of 2-cyanomethyl-2-adamantanol at a selectivity of 99.5%. This reaction liquid was dropwise added in 30 minutes to a solution of 47 ml (318 millimole) of methacrylic anhydride, 45 ml (320 millimole) of dried triethylamine and 100 ml of dried tetrahydrofuran while the solution was cooled to 0° C. on an ice and water bath. After further stirred at 0° C. for 30 minutes, 200 mol of water and 300 ml of diethyl ether were added thereto and stirred. This solution was transferred into a separating funnel of 2 liter to remove an aqueous phase, and then an organic phase was washed with diluted hydrochloric acid to remove a Li salt and a triethylamine salt. Further, this was neutralized by a sodium carbonate aqueous solution and then washed with water. The organic phase was dried on anhydrous magnesium sulfate, and then the solvent was distilled off by means of an evaporator to obtain 38 g of a crude reaction product. n-Hexane 100 ml was added to the crude reaction product, and the solution was cooled while stirring to remove deposited 2-cyanomethyl-2-adamantanol by filtration. Activated carbon was added to the n-hexane solution to confirm that the solution became colorless, and it was filtered off. Then, the solvent was distilled off by means of an evaporator to obtain a colorless liquid. It was analyzed by gas chromatography to confirm that the intended product having a purity of 97.0% was obtained at a yield of 35.0 g. The respective data of 1H-NMR, 13C-NMR and GC-MS are shown below.

Quelle