Dimethyl Sulfoxide → 2-Chloro-1,3-dicyclopropylpropane-1,3-dione

HRID 558318Notes

Reaction equation

HRID 558318 reaction equation
C[Si]([Cl:5])(C)C.[Br-].C([NH3+])(C)(C)C.[CH:12]1([C:15](=[O:22])[CH2:16][C:17]([CH:19]2[CH2:21][CH2:20]2)=[O:18])[CH2:14][CH2:13]1.CS(C)=O>C(#N)C.O>[Cl:5][CH:16]([C:17]([CH:19]1[CH2:20][CH2:21]1)=[O:18])[C:15]([CH:12]1[CH2:13][CH2:14]1)=[O:22]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6397ChlorotrimethylsilaneHCID 137807821,3-Dicyclopropylpropane-1,3-dioneHCID 21584498Tert-butyl ammonium bromide

Product 1

HCID 219498672-Chloro-1,3-dicyclopropylpropane-1,3-dioneYield 46.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent2×

Procedure

Trimethylsilyl chloride (16.6 ml, 130 mmol) was added to a solution of tert-butylammonium bromide (0.70 g, 2.17 mmol) in acetonitrile (50 ml) under nitrogen at 0° C. 1,3-Dicyclopropyl-propane-1,3-dione (ref: WO98155438) (6.62 g, 43.5 mmol) in acetonitrile (15 ml) was then added followed by dimethylsulfoxide (9.25 ml, 130 mmol) dropwise, and the reaction was allowed to warm to room temperature over 4 hours. The mixture was diluted with water (75 ml), extracted with diethylether (3×35 ml) and the combined organic extracts dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel eluting with pentane:diethylether (95:5, by volume) to provide the title compound (3.76 g) as an oil, which was an 80:20 mixture of enol:keto forms.

Workup

  1. extractionextracted with diethylether (3×35 ml)
  2. dry with materialthe combined organic extracts dried over magnesium sulphate
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was purified by flash chromatography on silica gel eluting with pentane:diethylether (95:5, by volume)

Sources & evidence

ORD record
ord-aeb7f42f3342488a987477240ef2c5ae
Source dataset
uspto-grants-2011_11
Patent number
US08063044B2

Reaction notes

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