Sodium Hydroxide → HCID 131733571, compound

HRID 1748923Notes

Reaction equation

HRID 1748923 reaction equation
[OH-].[Na+].[C:3]1([S+:9]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[OH:22][CH2:23][C:24]([F:30])([F:29])[S:25]([OH:28])(=[O:27])=[O:26].CS(O[CH2:36][C:37](=[CH2:52])[C:38]([O:40][C:41]12[CH2:50][CH:45]3[CH2:46][CH:47]([CH2:49][CH:43]([CH2:44]3)[CH:42]1[CH3:51])[CH2:48]2)=[O:39])(=O)=O>>[C:16]1([S+:9]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1.[CH3:51][CH:42]1[CH:43]2[CH2:44][CH:45]3[CH2:46][CH:47]([CH2:48][C:41]1([O:40][C:38]([C:37](=[CH2:36])[CH2:52][O:22][CH2:23][C:24]([F:30])([F:29])[S:25]([OH:28])(=[O:27])=[O:26])=[O:39])[CH2:50]3)[CH2:49]2

Participants

4

Reactant 3

HCID 14798Sodium HydroxideHCID 89428483HCID 89428483, compoundHCID 131733570HCID 131733570, compound

Product 1

HCID 131733571HCID 131733571, compoundYield 42%

Procedure

In a 500-ml three-neck flask, 39.8 g (45.6 mmol) of an aqueous solution of 5% sodium hydroxide and 16.1 g (38.0 mmol) of 2-hydroxy-1,1-difluoroethanesulfonic acid triphenylsulfonium were placed. The resulting solution was stirred for 10 minutes at room temperature, thereby completely dissolving the solid substance. Subsequently, 25 g of crude 2-methyladamantyl 2-[(methanesulfonyloxy)methyl]acrylate was dropped and mixed into the solution. The mixed solution was then stirred for 1 hour at room temperature. After the completion of the reaction, the thus-obtained reaction solution was separated into an aqueous layer and a target product layer. The aqueous layer was extracted with 45 g of chloroform. The target product layer was combined with the chloroform extract. The combined product layer was washed five times with 45 g of water, washed twice with 30 g of 0.1N hydrochloric acid and further washed twice with 45 g of water. The washed product layer was concentrated under reduced pressure to distill therefrom a major part of the organic solvent. The resulting product was purified by column chromatography and dissolved in 10 g of methyl ethyl ketone at 40° C. Into the product solution, 30 g of diisopropyl ether was slowly dropped. The product solution was stirred for 1 hour at room temperature. After confirming the deposition of a crystalline substance, the crystalline substance was filtered out and dried under reduced pressure. With this, 10.5 g of the target compound (PAG-2) was obtained as a white solid substance (purity: 96%, yield: 28%).

Workup

  1. dissolutioncompletely dissolving the solid substance
  2. additionmixed into the solution
  3. stirringThe mixed solution was then stirred for 1 hour at room temperature
  4. customAfter the completion of the reaction
  5. customthe thus-obtained reaction solution
  6. customwas separated into an aqueous layer
  7. extractionThe aqueous layer was extracted with 45 g of chloroform
  8. extractionextract
  9. washThe combined product layer was washed five times with 45 g of water
  10. washwashed twice with 30 g of 0.1N hydrochloric acid
  11. washfurther washed twice with 45 g of water
  12. concentrationThe washed product layer was concentrated under reduced pressure
  13. distillationto distill
  14. customThe resulting product was purified by column chromatography
  15. dissolutiondissolved in 10 g of methyl ethyl ketone at 40° C
  16. additionInto the product solution, 30 g of diisopropyl ether was slowly dropped
  17. stirringThe product solution was stirred for 1 hour at room temperature
  18. filtrationthe crystalline substance was filtered out
  19. customdried under reduced pressure

Sources & evidence

ORD record
ord-942e3e96f5fe42db9183cec334f43a34
Source dataset
uspto-grants-2015_10
Patent number
US09152045B2

Reaction notes

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