Methyl Ethyl Ketone → HCID 24888073, compound

HRID 661731Notes

Reaction equation

HRID 661731 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, compound2×

Product 1

HCID 24888073HCID 24888073, compoundYield 94%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 7909Methyl Isobutyl KetoneSolvent2×

Conditions

Temperature
45 °C

Procedure

Into a separable flask having an inner volume of 300 ml and equipped with a reflux condenser, a stiffer, a thermometer, and a nitrogen inlet were charged 30 ml of MIBK, 60 ml of DMSO, and 65 g (0.70 mol) of epichlorohydrin. After the atmosphere was displaced with nitrogen, 20.6 g (0.09 mol) of 1-(2,4-dihydroxyphenyl)adamantane synthesized in the above (1) was added and the mixture was heated to 45° C. with agitation. Into this solution, 7.6 g (0.19 mol) of sodium hydroxide was added over 0.5 hour, and the agitation was continued for another 0.5 hour. Then the temperature was raised to 65° C. and the agitation was continued for 2 hours. The reaction solution was cooled to room temperature, added with 25 ml of MIBK, and washed by water until the aqueous phase became neutral, and then the organic layer was concentrated to obtain yellowish viscous solution. The yellowish viscous solution was dissolved into 285 g of MEK, added with 3.4 g of 25% by mass of aqueous sodium hydroxide solution, and then heated under reflux with agitation for 2 hours. The solution was cooled to room temperature, washed with water until the aqueous phase became neutral from alkaline, and then the washing was done for two more times. The organic layer was concentrated to obtain the target compound (yield 94%). The LC (liquid chromatography) of this compound showed the purity of 95% (monomer content was 95% and the rests were oligomers of the target compound).

Workup

  1. customInto a separable flask having
  2. customan inner volume of 300 ml and equipped with a reflux condenser
  3. additionwas added
  4. temperatureThen the temperature was raised to 65° C.
  5. waitthe agitation was continued for 2 hours
  6. temperatureThe reaction solution was cooled to room temperature
  7. washwashed by water until the aqueous phase
  8. concentrationthe organic layer was concentrated
  9. customto obtain yellowish viscous solution
  10. temperatureheated
  11. temperatureunder reflux with agitation for 2 hours
  12. temperatureThe solution was cooled to room temperature
  13. washwashed with water until the aqueous phase
  14. concentrationThe organic layer was concentrated

Sources & evidence

ORD record
ord-24496a250d8b4f19990966fef02bf5f4
Source dataset
uspto-grants-2011_12
Patent number
US08084650B2

Reaction notes

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