Methyl Ethyl Ketone → 1,3-Bis(4-glycidyloxyphenyl)adamantane

HRID 1712185Notes

Reaction equation

HRID 1712185 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]23[CH2:17][CH:12]4[CH2:13][CH:14]([CH2:16][C:10]([C:18]5[CH:23]=[CH:22][C:21]([OH:24])=[CH:20][CH:19]=5)([CH2:11]4)[CH2:9]2)[CH2:15]3)=[CH:4][CH:3]=1.[CH2:25]([CH:27]1[O:29][CH2:28]1)Cl.[OH-].[Na+].C[CH2:33][C:34]([CH3:36])=[O:35]>CC(CC(C)=O)C.CS(C)=O>[CH2:25]([O:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]23[CH2:15][CH:14]4[CH2:13][CH:12]([CH2:11][C:10]([C:18]5[CH:19]=[CH:20][C:21]([O:24][CH2:33][CH:34]6[O:35][CH2:36]6)=[CH:22][CH:23]=5)([CH2:16]4)[CH2:9]2)[CH2:17]3)=[CH:6][CH:7]=1)[CH:27]1[O:29][CH2:28]1

Participants

7

Reactant 4

HCID 6569Methyl Ethyl KetoneHCID 7835EpichlorohydrinHCID 14798Sodium Hydroxide2×HCID 44543464,4'-(1,3-Adamantanediyl)diphenol

Product 1

HCID 187042671,3-Bis(4-glycidyloxyphenyl)adamantaneYield 92.9%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 7909Methyl Isobutyl KetoneSolvent2×

Conditions

Temperature
45 °C

Procedure

In a separable flask having an inner volume of 300 ml, equipped with a reflux condenser, a stirrer, and a thermometer, were charged 20.0 g (0.06 mol) of 1,3-bis(4-hydroxyphenyl)adamantane, 46 g (0.50 mol) of epichlorohydrin, 30 mL of MIBK, and 60 mL of DMSO, and they were heated to 45° C. Then, 5.5 g (0.14 mol) of sodium hydroxide was added into this solution by small portions during a period of 1.5 hours. After completion of the addition, the reaction temperature was raised to 75° C., and the reaction was carried out for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, added by 25 mL of MIBK, and washed with water until the aqueous layer became neutral. The resulting organic layer was concentrated to obtain pale yellow solids. The pale yellow solids were dissolved in 285 g of MEK, added by 3.4 g of 25% by mass of aqueous sodium hydroxide solution, and then the mixture was stirred for 2 hours under reflux. Thereafter, the solution was cooled to room temperature, and washed by water until the aqueous layer became neutral from alkaline. The water-washing was performed two more times, and then the organic layer was concentrated to obtain pale yellow solids, which was recrystallized by a mixed solvent of THF (tetrahydrofuran) and isopropyl ether to obtain 24.1 g of 1,3-bis(4-glycidyloxyphenyl)adamantane having the following formula (purity of 94% by LC (liquid chromatography), epoxy equivalent of 224).

Workup

  1. customIn a separable flask having
  2. customan inner volume of 300 ml, equipped with a reflux condenser, a stirrer
  3. additionAfter completion of the addition
  4. temperaturethe reaction temperature was raised to 75° C.
  5. temperaturethe mixture was cooled to room temperature
  6. washwashed with water until the aqueous layer
  7. concentrationThe resulting organic layer was concentrated
  8. customto obtain pale yellow solids
  9. temperatureunder reflux
  10. temperatureThereafter, the solution was cooled to room temperature
  11. washwashed by water until the aqueous layer
  12. washThe water-washing
  13. concentrationthe organic layer was concentrated
  14. customto obtain pale yellow solids, which
  15. customwas recrystallized by a mixed solvent of THF (tetrahydrofuran) and isopropyl ether

Sources & evidence

ORD record
ord-600bfbc63c874267a1f56223c354ce93
Source dataset
uspto-grants-2010_09
Patent number
US07790917B2

Reaction notes

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