Methanol → 2-Methyl-2-adamantyl methacrylate

HRID 1699135Notes

Reaction equation

HRID 1699135 reaction equation
[CH3:1][C:2]1([OH:12])[CH:9]2[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:11][CH:3]1[CH2:4]3)[CH2:8]2.[C:13](Cl)(=[O:17])[C:14]([CH3:16])=[CH2:15].C(N(CC)CC)C.CO>C(C(C)=O)C(C)C.O.O1CCCC1>[C:13]([O:12][C:2]1([CH3:1])[CH:3]2[CH2:11][CH:7]3[CH2:6][CH:5]([CH2:10][CH:9]1[CH2:8]3)[CH2:4]2)(=[O:17])[C:14]([CH3:16])=[CH2:15]

Participants

8

Reactant 4

HCID 887MethanolHCID 8471TriethylamineHCID 13528Methacryloyl chloride2×HCID 1365452-Methyl-2-adamantanol

Product 1

HCID 98375662-Methyl-2-adamantyl methacrylateYield 100.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 7909Methyl Isobutyl KetoneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

Into a reaction vessel were charged 116.41 g of tetrahydrofuran and 16.63 g (0.1 mol) of 2-methyl-2-adamantanol, and 21.56 g (0.2 mol) of methacryloyl chloride was poured thereto at -10° C. under stirring. To the mixture, 25.56 g (0.25 mol) of triethylamine was added dropwise and the resulting mixture was left as it was for 15 minutes. The mixture was heated up to 69° C., the refluxing temperature, and stirring was continued for 11 hours while maintaining the refluxing state to react the mixture. After cooling, 6.41 g (0.2 mol) of methanol was added dropwise at -10° C. to deactivate the unreacted methacryloyl chloride. Then, the mixture was diluted with 116.41 g of methy isobutyl ketone. To the mixture, 68.87 g of water was added to wash it and thereafter the mixture was separated into layers. To the organic layer was added 112 g of a saturated aqueous sodium chloride solution. The resulting mixture was neutralized, under ice cooling, with a 5% aqueous sulfuric acid solution so as to adjust pH to from 7 to 8 and thereafter the mixture was separated into layers. The organic layer after separation was concentrated at a bath temperature of 40° C. to yield 23.62 g of brown crude 2-methyl-2-adamantyl methacrylate.

Workup

  1. additionwas poured
  2. waitthe resulting mixture was left as it
  3. temperatureThe mixture was heated up to 69° C.
  4. stirringthe refluxing temperature, and stirring
  5. waitwas continued for 11 hours
  6. temperaturewhile maintaining the refluxing state
  7. customto react the mixture
  8. temperatureAfter cooling
  9. washto wash it
  10. customthe mixture was separated into layers
  11. additionTo the organic layer was added 112 g of a saturated aqueous sodium chloride solution
  12. customthe mixture was separated into layers
  13. customThe organic layer after separation
  14. concentrationwas concentrated at a bath temperature of 40° C.

Sources & evidence

ORD record
ord-ca2ad97b34654bcbbee23c70774024e7
Source dataset
uspto-grants-2002_02
Patent number
US06344582B1

Reaction notes

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