Reaktion #170953

ord-fd63c91c4c9a443d80e67e9653d27fce

Reaktionsgleichung

OC12CC3CC(O)(C1)CC(O)(C3)C2
1,3,5-adamantanetriol
O=S(=O)(O)O
sulfuric acid
COc1ccc(O)cc1
p-methoxyphenol
[Na+].[OH-]
sodium hydroxide
O=O
oxygen
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(O)(CC(O)(C3)C1)C2
3,5-dihydroxy-1-adamantyl methacrylate

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

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
    SonstigeThus, 3,5-dihydroxy-1-adamantyl methacrylate was synthesized
  8. 8
    SonstigeThe obtained reaction solution
  9. 9
    WaschenThe resultant organic phase was washed with 500 ml of ion exchange water twice
  10. 10
    Extraktionextraction
  11. 11
    workup.ADDITIONTo the ethyl acetate solution, 0.76 g of p-methoxyphenol was added as a polymerization inhibitor
  12. 12
    workup.DISSOLUTIONdissolved completely
  13. 13
    FiltrationPrecise filtration
  14. 14
    Filtrationfilter
  15. 15
    EinengenThen, the resultant solution was concentrated by use of an evaporator while the temperature of the solution
  16. 16
    Sonstigewas kept at 40° C., until the weight of the solution
  17. 17
    EinengenAfter the concentration
  18. 18
    Temperaturcooling
  19. 19
    Sonstigecrystallization
  20. 20
    Sonstigewas performed at a temperature of an ice water bath
  21. 21
    Sonstigeto separate the crystal
  22. 22
    Filtrationby filtration
  23. 23
    WaschenThe crystal was rinsed with ion exchange water twice
  24. 24
    Sonstigedried at a reduced pressure at 35° C. for 24 hours
  25. 25
    SonstigeDuring the process from the dehydration esterification reaction
  26. 26
    Sonstigeto the solid-liquid separation
  27. 27
    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 prepared gas introduction tube, 128.9 g of 1,3,5-adamantanetriol, 361 g of methacrylic acid, 1.7 g of concentrated sulfuric acid as an acid catalyst, 1.1 g of p-methoxyphenol as a polymerization inhibitor, 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 12 hours. Thus, 3,5-dihydroxy-1-adamantyl methacrylate was synthesized. 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. The resultant organic phase was washed with 500 ml of ion exchange water twice. After the water phase was all united, extraction was performed with 300 ml of ethyl acetate twice. To the ethyl acetate solution, 0.76 g of p-methoxyphenol was added as a polymerization inhibitor and dissolved completely. Precise filtration was performed by use of a Teflon® filter having a pore diameter of 0.1 μm. Then, the resultant solution was concentrated 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 ion exchange water 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 3,5-dihydroxy-1-adamantyl methacrylate. Tetrahydrofuran was used as the solvent for measuring the turbidity.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08846840B2uspto-grants-2014_09