Water → Triphenylsulfonium ((1-adamantyl)methoxycarbonyl)difluoromethanesulfonate

HRID 84979

Reaction equation

HRID 84979 reaction equation
C([NH3+])(C)(C)C.[C:6]12([CH2:16][O:17][C:18]([C:20]([F:26])([F:25])[S:21]([O-:24])(=[O:23])=[O:22])=[O:19])[CH2:15][CH:10]3[CH2:11][CH:12]([CH2:14][CH:8]([CH2:9]3)[CH2:7]1)[CH2:13]2.O.[Br-].[C:29]1([S+:35]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>C(Cl)(Cl)Cl>[C:6]12([CH2:16][O:17][C:18]([C:20]([F:26])([F:25])[S:21]([O-:24])(=[O:22])=[O:23])=[O:19])[CH2:15][CH:10]3[CH2:9][CH:8]([CH2:14][CH:12]([CH2:11]3)[CH2:13]1)[CH2:7]2.[C:42]1([S+:35]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1

Participants

5

Reactant 3

HCID 962WaterHCID 11984010Triphenylsulfonium BromideHCID 131731911(Adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt

Product 1

HCID 44224732Triphenylsulfonium ((1-adamantyl)methoxycarbonyl)difluoromethanesulfonateYield 92%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Within a 1-L three-neck flask, 122 g (purity: 99%, 307 mmol, 1.0 eq) of the (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt obtained in Example 5-b was dissolved in 500 g of chloroform. To the resulting solution, 400 g of water and 110.5 g (322 mmol, 1.05 eq) of triphenylsulfonium bromide were added. This reaction solution was stirred for 1 hour. After the reaction, the reaction solution was separated into an organic layer and an aqueous layer. The organic layer was washed with water, followed by distillating chloroform from the washed organic layer. The thus-obtained concentrated solution was dissolved in a mixed solvent of chloroform, ethyl acetate and diisopropyl ether and then recrystallized. With this, 166 g of target triphenylsulfonium (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonate was obtained (yield: 92%, purity: 99%). No fluorine ion (F−) was detected from any liquid waste of this step. Further, 200 ppb of sodium ion (Na+) was detected from the triphenylsulfonium (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonate obtained in this step.

Workup

  1. customAfter the reaction
  2. customthe reaction solution was separated into an organic layer
  3. washThe organic layer was washed with water
  4. dissolutionThe thus-obtained concentrated solution was dissolved in a mixed solvent of chloroform, ethyl acetate and diisopropyl ether
  5. customrecrystallized

Sources & evidence

ORD record
ord-acfa2cd248d44fc8bd2cb4c3be34f306
Source dataset
uspto-grants-2014_09
Patent number
US08846966B2

Linked notes

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