Trichloroacetyl chloride → (RS)-3-benzyl-2,2-dichlorocyclobutanone

HRID 1280750Notes

Reaction equation

HRID 1280750 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH:2]=[CH2:3].[Cl:10][C:11]([Cl:16])(Cl)[C:12](Cl)=[O:13].P(Cl)(Cl)(Cl)=O>C(OCC)C.[Cu].[Zn]>[CH2:1]([CH:2]1[CH2:3][C:12](=[O:13])[C:11]1([Cl:16])[Cl:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 6420Trichloroacetyl chlorideHCID 9309AllylbenzeneHCID 24813Phosphorus oxychloride

Product 1

HCID 18425787(RS)-3-benzyl-2,2-dichlorocyclobutanoneYield 20%

Reagents, catalysts & solvents 2

HCID 10290809Zinc copper coupleCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To a room temperature mixture containing allylbenzene (1.84 g, 15.6 mmol), zinc-copper couple (5.1 g, 78 mmol) and diethylether (60 ml) was added dropwise a solution of trichloroacetylchloride (2.96 ml, 26.5 mmol) and phosphorus oxychloride (2.46 ml, 26.5 mmol) in diethylether (20 ml). The reaction mixture was stirred at room temperature for 1 hour, filtered and the filtrate was partially concentrated. The residue was neutralized with saturated NaHCO3. The aqueous phase was extracted with diethylether. The combined organic phases were washed successively with H2O and brine, dried over Na2SO4, and concentrated. The residue was chromatographed over silica gel (hexane) to provide (RS)-3-benzyl-2,2-dichlorocyclobutanone (0.71 g, 20%) as a yellow oil, MS: m/e=228.1 (M-H+).

Workup

  1. filtrationfiltered
  2. concentrationthe filtrate was partially concentrated
  3. extractionThe aqueous phase was extracted with diethylether
  4. washThe combined organic phases were washed successively with H2O and brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was chromatographed over silica gel (hexane)

Sources & evidence

ORD record
ord-aed1c7b77c754df9b4747f0e8f78d895
Source dataset
uspto-grants-2002_09
Patent number
US06451819B2

Reaction notes

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