Methyl Ethyl Ketone → HCID 24888073, compound

HRID 1712186Notes

Reaction equation

HRID 1712186 reaction equation
[CH2:1]([CH:3]1[O:5][CH2:4]1)Cl.[OH:6][C:7]1[CH:12]=[C:11]([OH:13])[CH:10]=[CH:9][C:8]=1[C:14]12[CH2:23][CH:18]3[CH2:19][CH:20]([CH2:22][CH:16]([CH2:17]3)[CH2:15]1)[CH2:21]2.[OH-].[Na+].C[CH2:27][C:28]([CH3:30])=[O:29]>CC(CC(C)=O)C.CS(C)=O>[CH2:1]([O:6][C:7]1[CH:12]=[C:11]([O:13][CH2:27][CH:28]2[O:29][CH2:30]2)[CH:10]=[CH:9][C:8]=1[C:14]12[CH2:15][CH:16]3[CH2:22][CH:20]([CH2:19][CH:18]([CH2:17]3)[CH2:23]1)[CH2:21]2)[CH:3]1[O:5][CH2:4]1

Participants

7

Reactant 4

HCID 6569Methyl Ethyl KetoneHCID 7835EpichlorohydrinHCID 14798Sodium Hydroxide2×HCID 15105171HCID 15105171, compound

Product 1

HCID 24888073HCID 24888073, compoundYield 88.2%

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, a thermometer, and a nitrogen inlet were charged 30 mL of MIBK, 60 mL of DMSO, and 65 g (0.70 mol) of epichlorohydrin, and the atmosphere of the system was displaced by nitrogen. Then, 20.6 g (0.09 mol) of 1-(2,4-dihydroxyphenyl)adamantane was added and the mixture was heated to 45° C. with stirring. Then, 7.6 g (0.19 mol) of sodium hydroxide was added into this solution by small portions during a period of 0.5 hour, and the agitation was continued for further 2 hours. Thereafter, the reaction solution was cooled to room temperature, added by 25 mL of MIBK, and washed by water until the aqueous layer became neutral. The resulting organic layer was concentrated to obtain viscous liquid having a pale yellow color. The viscous liquid having a pale yellow color was 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 28.3 g of 1-(2,4-diglycidyloxyphenyl)adamantane having the following formula (93% purity by LC, epoxy equivalent of 185).

Workup

  1. customIn a separable flask having
  2. customan inner volume of 300 ml, equipped with a reflux condenser, a stirrer
  3. temperatureThereafter, the reaction solution was cooled to room temperature
  4. washwashed by water until the aqueous layer
  5. concentrationThe resulting organic layer was concentrated
  6. customto obtain viscous liquid
  7. stirringthe mixture was stirred for 2 hours
  8. temperatureunder reflux
  9. temperatureThereafter, the solution was cooled to room temperature
  10. washwashed by water until the aqueous layer
  11. washThe water-washing
  12. concentrationthe organic layer was concentrated

Sources & evidence

ORD record
ord-25375ba9ad73466c8a3562862df3da3d
Source dataset
uspto-grants-2010_09
Patent number
US07790917B2

Reaction notes

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