Реакция #170952

Уравнение реакции

1,3-adamantanediol

p-methoxyphenol

sulfuric acid

sodium hydroxide

oxygen

p-methoxyphenol

methacrylic acid

sulfuric acid

methacrylic acid

→

3-hydroxy-1-adamantyl methacrylate

Растворители

water

toluene

water

water

Условия реакции

Обработка

1. 1
   ДругоеTo a 2 L jacket-equipped separable flask
2. 2
   Другоеprovided with a stirrer
3. 3
   ДругоеPrepared gas
4. 4
   workup.ADDITIONdiluted with nitrogen so as
5. 5
   ТемператураWhile the solution was heated
6. 6
   Другоеwas removed by the Dean-Stark water separator
7. 7
   workup.ADDITIONThus, a reaction solution containing 3-hydroxy-1-adamantyl methacrylate
8. 8
   Другоеwas obtained
9. 9
   ДругоеThe obtained reaction solution
10. 10
    ПромывкаThe resultant solution was washed with 5% by weight of dilute sulfuric acid and with 500 ml of ion exchange water
11. 11
    ФильтрацияAfter the washing, precise filtration
12. 12
    Фильтрацияfilter
13. 13
    ДругоеThen, concentration-crystallization
14. 14
    Другоеwas performed by use of an evaporator while the temperature of the solution
15. 15
    Другоеwas kept at 40° C., until the weight of the solution
16. 16
    КонцентрированиеAfter the concentration
17. 17
    Температураcooling
18. 18
    Другоеcrystallization
19. 19
    Другоеwas performed at a temperature of an ice water bath
20. 20
    Другоеto separate the crystal
21. 21
    Фильтрацияby filtration
22. 22
    ПромывкаThe crystal was rinsed with heptane twice
23. 23
    Другоеdried at a reduced pressure at 35° C. for 24 hours
24. 24
    ДругоеDuring the process from the dehydration esterification reaction
25. 25
    Другоеto the solid-liquid separation
26. 26
    Промывкаuntil the termination of rinsing

Методика

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.

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