Trichloroacetyl chloride → 3-((Benzyloxy)methyl)cyclobutanone

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Reaction Steps

Into a 200 ml four-necked flask, copper(II) acetate monohydrate (0.16 g) was added and dissolved in 5 ml of acetic acid. Zinc powder (2.8 g) was added to this solution, and after allowing the mixture to stir for 90 seconds, decantation was carried out. Acetic acid (1 ml) was added to the residue and decantation was repeated five times. Dry diethyl ether (6 ml) was added to the residue and decantation was repeated three times. The atmosphere in the reaction vessel was completely replaced with argon gas by operating a three-way stopcock that was connected to an aspirator. Allyl benzyl ether 6.3 g (6.3 ml, 40.5 mmol) dissolved in 60 ml of dry diethyl ether was placed in this reaction vessel. Trichloroacetyl chloride 5.0 ml (45 mmol) and phosphoryl trichloride 4.1 ml (45 mmol) that were dissolved in 40 ml of dry diethyl ether were added dropwise to the above solution over a period of one hour. This reaction solution was refluxed and stirred for 21 hours. After the reaction solution was returned to room temperature, it was filtered. The filtrate was quenched by the addition of water and washed with water and brine. The organic layer was dehydrated over anhydrous sodium sulfate and then concentrated. Acetic acid (33 ml) and zinc powder (13.3 g) were added to the residue, and the mixture was stirred under reflux for 4 hours. This reaction solution was filtered and the filtrate was concentrated. This residue was dissolved in ethyl acetate, and zinc powder precipitated upon neutralization with a saturated NaHCO3 solution was separated by filtration using Celite. The filtrate was separated into two layers and washed with a saturated NaHCO3 solution and brine. The organic layer was dehydrated over sodium sulfate and then concentrated. The unreacted allyl benzyl ether was removed by evaporation under reduced pressure in a glass tube oven. The residue was purified by silica gel chromatography (toluene:ethyl acetate=96:4) to obtain 3-(benzyloxymethyl)cyclobutanone (2.41 g, 29%) as a clear oil. A clear oil: b.p. 115° C./1.0 mmHg. (TLC; Rf=0.20 (G):(M))

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