4'-Fluoroacetophenone → 2-[1-(4-Fluorophenyl)ethylidene]-1,3-dithiolane

HRID 1708998Notes

Reaction equation

HRID 1708998 reaction equation
C([Li])CCC.C(OP([CH:14]1[S:18][CH2:17][CH2:16][S:15]1)(OCC)=O)C.[CH3:19][C:20]([C:22]1[CH:27]=[CH:26][C:25]([F:28])=[CH:24][CH:23]=1)=O>CCCCCC.O1CCCC1>[S:18]1[CH2:17][CH2:16][S:15][C:14]1=[C:20]([C:22]1[CH:27]=[CH:26][C:25]([F:28])=[CH:24][CH:23]=1)[CH3:19]

Participants

6

Reactant 3

HCID 98284'-FluoroacetophenoneHCID 133020352-Diethoxyphosphoryl-1,3-dithiolaneHCID 178418339Butyllithium

Product 1

HCID 133020362-[1-(4-Fluorophenyl)ethylidene]-1,3-dithiolane

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A 1.3M solution of n-butyllithium in hexane (28 ml) is added at -78° to a solution of 2-diethoxyphosphoryl-1,3-dithiolane (8.1 g) in dry tetrahydrofuran (70 ml). The mixture is stirred for one hour at -78° and 4-fluoroacetophenone is added (4.3 g). The mixture is stirred for one more hour at the same temperature and slowly warmed to room temperature. After removal of the solvents, the residue is dissolved in dichloromethane (200 ml). The solution is washed with a 10% aqueous solution of ammonium chloride (3×100 ml) and with water (2×100 ml), dried over magnesium sulphate and evaporated in vacuo. The oily residue is purified by column chromatography on silica gel using hexane/toluene 1:1 as eluant. The product is dried in vacuo to constant weight to yield 1-(1,3-dithiolan-2-ylidene)-1-(4-fluorophenyl)-ethane, m.p. 27°-31°.

Workup

  1. stirringThe mixture is stirred for one more hour at the same temperature
  2. customAfter removal of the solvents
  3. dissolutionthe residue is dissolved in dichloromethane (200 ml)
  4. washThe solution is washed with a 10% aqueous solution of ammonium chloride (3×100 ml) and with water (2×100 ml)
  5. dry with materialdried over magnesium sulphate
  6. customevaporated in vacuo
  7. customThe oily residue is purified by column chromatography on silica gel
  8. customThe product is dried in vacuo to constant weight

Sources & evidence

ORD record
ord-86f020658fd44c9e87c60232f80c96dd
Source dataset
uspto-grants-1990_08
Patent number
US04946861

Reaction notes

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