Triethylamine → Triphenylsulfonium 2-(2,2-dimethylpropionyloxy)-3,3,3-trifluoro-2-trifluoromethylpropane-1-sulfonate

HRID 2061313Notes

Reaction equation

HRID 2061313 reaction equation
[F:1][C:2]([F:15])([F:14])[C:3]([OH:13])([C:9]([F:12])([F:11])[F:10])[CH2:4][S:5]([O-:8])(=[O:7])=[O:6].[C:16]1([S+:22]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C(N(CC)CC)C.[C:42](Cl)(=[O:47])[C:43]([CH3:46])([CH3:45])[CH3:44]>CN(C)C1C=CN=CC=1.C(Cl)Cl>[CH3:44][C:43]([CH3:46])([CH3:45])[C:42]([O:13][C:3]([C:2]([F:1])([F:14])[F:15])([C:9]([F:12])([F:10])[F:11])[CH2:4][S:5]([O-:8])(=[O:7])=[O:6])=[O:47].[C:29]1([S+:22]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 62493Pivaloyl chlorideHCID 86644254Triphenylsulfonium 3,3,3-trifluoro-2-hydroxy-2-trifluoromethylpropane-1-sulfonate

Product 1

HCID 86644256Triphenylsulfonium 2-(2,2-dimethylpropionyloxy)-3,3,3-trifluoro-2-trifluoromethylpropane-1-sulfonateYield 59.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

Into a mixture solution of 2.6 g (5 mmoles) of triphenylsulfonium 3,3,3-trifluoro-2-hydroxy-2-trifluoromethylpropane-1-sulfonate prepared in Synthesis Example 1-9, 0.63 g (6 mmoles) of triethylamine, 0.12 g (1 mmole) of 4-dimethylaminopyridine, and 15 g of methylene chloride was added 0.72 g (6 mmoles) of pivaloyl chloride, and they were stirred at room temperature for 8 hours. Thereafter, the reaction was terminated by adding 11 g of 5% hydrochloric acid, and then the organic layer was separated, washed by water, and concentrated under reduced pressure. Into the concentrated solution was added a mixture solution of methyl isobutyl ketone and methylene chloride, and the resulted mixture was concentrated again under reduced pressure to distil the remaining water out. The obtained residue was recrystallized by adding diisopropyl ether, and then the crystals were recovered and dried to obtain the intended triphenylsulfonium 2-(2,2-dimethylpropionyloxy)-3,3,3-trifluoro-2-trifluoromethylpropane-1-sulfonate (1.8 g of white crystals (yield 58%)). The structure of the intended product is shown below.

Workup

  1. customThereafter, the reaction was terminated
  2. additionby adding 11 g of 5% hydrochloric acid
  3. customthe organic layer was separated
  4. washwashed by water
  5. concentrationconcentrated under reduced pressure
  6. additionInto the concentrated solution was added a mixture solution of methyl isobutyl ketone and methylene chloride
  7. concentrationthe resulted mixture was concentrated again under reduced pressure
  8. customto distil the remaining water out
  9. customThe obtained residue was recrystallized
  10. additionby adding diisopropyl ether
  11. customthe crystals were recovered
  12. customdried

Sources & evidence

ORD record
ord-3cf865ca389a4db080f397d64af191ba
Source dataset
uspto-grants-2012_10
Patent number
US08283104B2

Reaction notes

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