Sodium Hydroxide → HCID 131733569, compound

HRID 1748922Notes

Reaction equation

HRID 1748922 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].Br[CH2:32][C:33](=[CH2:41])[C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35]>C(#N)C>[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.[C:37]([O:36][C:34]([C:33](=[CH2:32])[CH2:41][O:22][CH2:23][C:24]([F:30])([F:29])[S:25]([OH:28])(=[O:27])=[O:26])=[O:35])([CH3:40])([CH3:39])[CH3:38]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 10955115Tert-butyl 2-(bromomethyl)prop-2-enoateHCID 131733570HCID 131733570, compound

Product 1

HCID 131733569HCID 131733569, compoundYield 88%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

In a 100-ml flask, 31 g of an aqueous solution of 5 mass % sodium hydroxide was placed. The solution was cooled, with stirring, by immersing the flask in an ice water bath. Then, 15.0 g of 2-hydroxy-1,1-difluoroethanesulfonic acid triphenylsulfonium (purity: 95%, 0.035 mol) was gradually added to the solution. The solution was returned to room temperature and stirred for 30 minutes. The solution was again cooled by immersing the flask in the ice water bath. After that, a solution of 6.5 g of tert-butyl 2-bromomethylacrylate (0.029 mol) in 10 g of acetonitrile was dropped into the above solution. The mixed solution was further stirred for 1.5 hours at room temperature. The thus-obtained reaction solution was separated into upper and lower layers. The lower layer was mixed with 20 g of chloroform and washed three times with 24 g of water. The resulting solution was solidified by concentration under reduced pressure. The solid product was dissolved in 10 g of methyl ethyl ketone at 40° C. Into the product solution, 25 g of diisopropyl ether was slowly dropped. The product solution was then 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 g of the target compound (PAG-1) was obtained as a white solid substance (purity: 99%, yield: 88%).

Workup

  1. temperatureThe solution was cooled
  2. customwas returned to room temperature
  3. stirringstirred for 30 minutes
  4. temperatureThe solution was again cooled
  5. stirringThe mixed solution was further stirred for 1.5 hours at room temperature
  6. customThe thus-obtained reaction solution
  7. customwas separated into upper and lower layers
  8. additionThe lower layer was mixed with 20 g of chloroform
  9. washwashed three times with 24 g of water
  10. concentrationThe resulting solution was solidified by concentration under reduced pressure
  11. dissolutionThe solid product was dissolved in 10 g of methyl ethyl ketone at 40° C
  12. additionInto the product solution, 25 g of diisopropyl ether was slowly dropped
  13. stirringThe product solution was then stirred for 1 hour at room temperature
  14. filtrationthe crystalline substance was filtered out
  15. customdried under reduced pressure

Sources & evidence

ORD record
ord-3ee58968d5494f62b5e72b85ce8afec6
Source dataset
uspto-grants-2015_10
Patent number
US09152045B2

Reaction notes

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