Reaktion #170952

Reaktionsgleichung

1,3-adamantanediol

p-methoxyphenol

sulfuric acid

sodium hydroxide

oxygen

p-methoxyphenol

methacrylic acid

sulfuric acid

methacrylic acid

→

3-hydroxy-1-adamantyl methacrylate

Lösungsmittel

water

toluene

water

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeTo a 2 L jacket-equipped separable flask
2. 2
   Sonstigeprovided with a stirrer
3. 3
   SonstigePrepared gas
4. 4
   workup.ADDITIONdiluted with nitrogen so as
5. 5
   TemperaturWhile the solution was heated
6. 6
   Sonstigewas removed by the Dean-Stark water separator
7. 7
   workup.ADDITIONThus, a reaction solution containing 3-hydroxy-1-adamantyl methacrylate
8. 8
   Sonstigewas obtained
9. 9
   SonstigeThe obtained reaction solution
10. 10
    WaschenThe resultant solution was washed with 5% by weight of dilute sulfuric acid and with 500 ml of ion exchange water
11. 11
    FiltrationAfter the washing, precise filtration
12. 12
    Filtrationfilter
13. 13
    SonstigeThen, concentration-crystallization
14. 14
    Sonstigewas performed by use of an evaporator while the temperature of the solution
15. 15
    Sonstigewas kept at 40° C., until the weight of the solution
16. 16
    EinengenAfter the concentration
17. 17
    Temperaturcooling
18. 18
    Sonstigecrystallization
19. 19
    Sonstigewas performed at a temperature of an ice water bath
20. 20
    Sonstigeto separate the crystal
21. 21
    Filtrationby filtration
22. 22
    WaschenThe crystal was rinsed with heptane twice
23. 23
    Sonstigedried at a reduced pressure at 35° C. for 24 hours
24. 24
    SonstigeDuring the process from the dehydration esterification reaction
25. 25
    Sonstigeto the solid-liquid separation
26. 26
    Waschenuntil the termination of rinsing

Vorschrift

To a 2 L jacket-equipped separable flask provided with a stirrer, a thermometer, a Dean-Stark water separator, a Dimroth condenser and a gas blowing tube, 84.0 g of 1,3-adamantanediol, 124.1 g of methacrylic acid, 0.38 g of p-methoxyphenol as a polymerization inhibitor, 1.2 g of concentrated sulfuric acid as an acid catalyst, and 750 ml of toluene as a solvent were put. Prepared gas diluted with nitrogen so as to have an oxygen concentration of about 5% by volume was supplied at a rate of 0.2 L/min. The reaction operation was performed as follows. While the solution was heated and water generated as a secondary product was removed by the Dean-Stark water separator, the reflux state was continued for 5 hours. Thus, a reaction solution containing 3-hydroxy-1-adamantyl methacrylate was obtained. The obtained reaction solution was cooled down to room temperature, and then a 10% by weight of aqueous solution of sodium hydroxide was added while stirring to neutralize the residual methacrylic acid and sulfuric acid. Then, the neutralized water phase was drawn out from the two-phase solution. To the residual organic phase, 0.85 g of p-methoxyphenol was added as a polymerization inhibitor. The resultant solution was washed with 5% by weight of dilute sulfuric acid and with 500 ml of ion exchange water, twice for each. After the washing, precise filtration was performed by use of a Teflon® filter having a pore diameter of 0.1 μm. Then, concentration-crystallization was performed by use of an evaporator while the temperature of the solution was kept at 40° C., until the weight of the solution became 110 g. After the concentration was finished, cooling crystallization was performed at a temperature of an ice water bath to separate the crystal by filtration. The crystal was rinsed with heptane twice, and then dried at a reduced pressure at 35° C. for 24 hours. During the process from the dehydration esterification reaction to the solid-liquid separation and until the termination of rinsing performed by use of ion exchange water, the prepared gas was kept blown into the solution. Table 1 shows the analysis results of the obtained 3-hydroxy-1-adamantyl methacrylate. Methylethylketone was used as the solvent for measuring the turbidity.

Quelle