18-Crown-6 → (E,E)-(3,7,11-Trimethyl-2,6,10-dodecatrienyl) (trifluoromethyl)sulfone

HRID 1885415Notes

Reaction equation

HRID 1885415 reaction equation
[CH2:1](Br)[CH:2]=[C:3]([CH2:5][CH2:6][CH:7]=[C:8]([CH2:10][CH2:11][CH:12]=[C:13]([CH3:15])[CH3:14])[CH3:9])[CH3:4].[F:17][C:18]([S:21]([O-:23])=[O:22])([F:20])[F:19].[K+].C1OCCOCCOCCOCCOCCOC1>CN(C)C=O>[CH3:4]/[C:3](/[CH2:5][CH2:6]/[CH:7]=[C:8](\[CH3:9])/[CH2:10][CH2:11][CH:12]=[C:13]([CH3:15])[CH3:14])=[CH:2]\[CH2:1][S:21]([C:18]([F:20])([F:19])[F:17])(=[O:23])=[O:22]

Participants

5

Reactant 3

HCID 2855718-Crown-6HCID 550199Farnesyl bromideHCID 2733643Potassium trifluoromethanesulphinate

Product 1

HCID 10914716(E,E)-(3,7,11-Trimethyl-2,6,10-dodecatrienyl) (trifluoromethyl)sulfoneYield 63%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 12.20 g (42.8 mmol) of Part B farnesyl bromide, 8.0 g (52 mmol, 1.2 equiv) of potassium trifluoromethylsulfinate (Parrish Chemical) and 1.00 g (4.3 mmol, 0.1 equiv) of 18-crown-6 in 200 mL of dry dimethylformamide was stirred for 66 hours. The dimethylformamide was evaporated at reduced pressure with minimal warming. The residue was dissolved in 600 mL of diethyl ether and washed with three 70 mL portions of H2O and 70 mL of brine, dried over MgSO4 and evaporated. Purification by flash chromatography on 200 g of Merck 9385 silica eluted with 15:85 CH2Cl2 : hexane provided 1.35 g of mixed fractions and 9.02 g (63%) of pure product. The mixed fractions were rechromatographed on 60 g of silica gel, eluting with 15:85 CH2Cl2 : hexane to provide 0.95 g (7%) of pure title product. The two portions of pure title triflone product were combined: 9.97 g (70%) of a pale yellow oil.

Workup

  1. customThe dimethylformamide was evaporated at reduced pressure with minimal warming
  2. dissolutionThe residue was dissolved in 600 mL of diethyl ether
  3. washwashed with three 70 mL portions of H2O and 70 mL of brine
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customPurification by flash chromatography on 200 g of Merck 9385 silica
  7. washeluted with 15:85 CH2Cl2

Sources & evidence

ORD record
ord-08d925dbc0c94af8a8030fa324b9288f
Source dataset
uspto-grants-1992_09
Patent number
US05144080

Reaction notes

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