反応 #170952

ord-cd9f2d93171e44769130843b0329e994

反応方程式

OC12CC3CC(C1)CC(O)(C3)C2
1,3-adamantanediol
COc1ccc(O)cc1
p-methoxyphenol
O=S(=O)(O)O
sulfuric acid
[Na+].[OH-]
sodium hydroxide
O=O
oxygen
COc1ccc(O)cc1
p-methoxyphenol
C=C(C)C(=O)O
methacrylic acid
O=S(=O)(O)O
sulfuric acid
C=C(C)C(=O)O
methacrylic acid
C=C(C)C(=O)OC12CC3CC(CC(O)(C3)C1)C2
3-hydroxy-1-adamantyl methacrylate

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他To a 2 L jacket-equipped separable flask
  2. 2
    その他provided with a stirrer
  3. 3
    その他Prepared gas
  4. 4
    workup.ADDITIONdiluted with nitrogen so as
  5. 5
    温度While the solution was heated
  6. 6
    その他was removed by the Dean-Stark water separator
  7. 7
    workup.ADDITIONThus, a reaction solution containing 3-hydroxy-1-adamantyl methacrylate
  8. 8
    その他was obtained
  9. 9
    その他The obtained reaction solution
  10. 10
    洗浄The resultant solution was washed with 5% by weight of dilute sulfuric acid and with 500 ml of ion exchange water
  11. 11
    ろ過After the washing, precise filtration
  12. 12
    ろ過filter
  13. 13
    その他Then, concentration-crystallization
  14. 14
    その他was performed by use of an evaporator while the temperature of the solution
  15. 15
    その他was kept at 40° C., until the weight of the solution
  16. 16
    濃縮After the concentration
  17. 17
    温度cooling
  18. 18
    その他crystallization
  19. 19
    その他was performed at a temperature of an ice water bath
  20. 20
    その他to separate the crystal
  21. 21
    ろ過by filtration
  22. 22
    洗浄The crystal was rinsed with heptane twice
  23. 23
    その他dried at a reduced pressure at 35° C. for 24 hours
  24. 24
    その他During the process from the dehydration esterification reaction
  25. 25
    その他to the solid-liquid separation
  26. 26
    洗浄until the termination of rinsing

実験手順

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.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US08846840B2uspto-grants-2014_09