Methanesulfonic Acid → HCID 86702732, compound

HRID 1530737Notes

Reaction equation

HRID 1530737 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(OC(C)C)(C)C.[C:20]([O:25][CH2:26][CH2:27][N:28]=[C:29]=[O:30])(=[O:24])[C:21]([CH3:23])=[CH2:22].CS(O)(=O)=O.C([O-])(O)=O.[Na+]>CCCCCC>[C:20]([O:25][CH2:26][CH2:27][NH:28][C:29](=[O:30])[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:24])[C:21]([CH3:23])=[CH2:22]

Participants

7

Reactant 5

HCID 6395Methanesulfonic AcidHCID 7914Diisopropyl EtherHCID 354092-Isocyanatoethyl methacrylateHCID 1365452-Methyl-2-adamantanolHCID 516892Sodium Bicarbonate

Product 1

HCID 86702732HCID 86702732, compoundYield 39.5%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
5.5 °C

Procedure

In a three-necked flask having an inner volume of 50 mL equipped with a thermometer and a stirring apparatus were charged 1.66 g (9.98 mmol) of 2-methyl-2-adamantanol, 2.0 mg of 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, 6.7 g of isopropyl ether, and 1.66 g (10.5 mmol) of 2-methacryloyloxyethyl isocyanate. After the mixture was cooled by ice water to an inner temperature of 5° C., 290 mg (3.0 mmol) of methanesulfonic acid was added dropwise. After stirring the reaction mixture for 15 hours with the reaction temperature maintained at 5 to 6° C., 10 g of a saturated aqueous NaHCO3 solution was added dropwise with the inner temperature maintained at 10° C. or less and, after completion of the dropwise addition, the mixture was allowed to stand still for 30 minutes. The organic layer (upper layer) formed was separated and the aqueous layer (lower layer) was extracted twice with 10 g of isopropyl ether. All the separated organic layers were combined, washed with 10 g of distilled water, and the organic layer concentrated under reduced pressure to obtain 2.82 g of a concentrate. The concentrate was dissolved in 15 g of hexane at 30° C. and the solution was cooled to −10° C. at a rate of 10° C./hour. The crystals which precipitated were separated by filtration and the crystals obtained were dried under vacuum (26.7 Pa) at 30° C. for 2 hours to obtain 1.29 g (purity 98.2%, 3.94 mmol, yield: 39.5%) of 2-methyladamantan-2-yl (2-methacryloyloxyethyl)carbamate.

Workup

  1. customIn a three-necked flask having
  2. customan inner volume of 50 mL equipped with a thermometer
  3. additionwas added dropwise
  4. temperaturemaintained at 10° C. or less
  5. additionafter completion of the dropwise addition
  6. waitto stand still for 30 minutes
  7. customThe organic layer (upper layer) formed
  8. customwas separated
  9. extractionthe aqueous layer (lower layer) was extracted twice with 10 g of isopropyl ether
  10. washwashed with 10 g of distilled water
  11. concentrationthe organic layer concentrated under reduced pressure
  12. customto obtain 2.82 g of a concentrate
  13. temperaturethe solution was cooled to −10° C. at a rate of 10° C./hour
  14. customThe crystals which precipitated
  15. customwere separated by filtration
  16. customthe crystals obtained
  17. customwere dried under vacuum (26.7 Pa) at 30° C. for 2 hours

Sources & evidence

ORD record
ord-3c8f661f55a24c5c831cebe4748022e6
Source dataset
uspto-grants-2015_07
Patent number
US09091917B2

Reaction notes

Loading…