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

To a diethyl ether (100 mL) solution of allyl benzyl ether (11.1 g, 75.0 mmol), was added zinc copper couple (74.5 g, 33.0 mmol) while stirring at room temperature, a dimethoxyethane (100 mL) solution of trichloroacetyl chloride (43.6 mL, 375 mmol) was added dropwise, and the mixture was stirred at mom temperature for six hours. The reaction mixture was poured into ice-cooled aqueous sodium hydrogencarbonate (500 mL), extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The mixture was filtered and then the solvent in the filtrate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of n-heptane and ethyl acetate: n-heptane/ethyl acetate=15/1). The obtained dichloro product was dissolved in methanol (200 mL), ammonium chloride (20.0 g, 375 mmol) was added and zinc powder (30.0 g, 450 mmol) was added little by little while vigorously stirring. After the reaction was completed, the insoluble matters were filtered off with Celite, the filtrate was distilled off under reduced pressure. Water was added to the residue, which was extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The mixture was filtered, and the solvent in the filtrate was then distilled off under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of n-heptane and ethyl acetate: n-heptane/ethyl acetate=15/1 then 12/1) to obtain the title compound (7.20 g, 37.9 mmol).

1. stirringthe mixture was stirred at mom temperature for six hours
2. additionThe reaction mixture was poured into ice-
3. extractionextracted with ethyl acetate
4. dry with materialdried over anhydrous magnesium sulfate
5. filtrationThe mixture was filtered
6. distillationthe solvent in the filtrate was distilled off under reduced pressure
7. customThe residue was purified by silica gel column chromatography (a mixed solvent of n-heptane and ethyl acetate
8. dissolutionThe obtained dichloro product was dissolved in methanol (200 mL)
9. stirringwhile vigorously stirring
10. filtrationthe insoluble matters were filtered off with Celite
11. distillationthe filtrate was distilled off under reduced pressure
12. additionWater was added to the residue, which
13. extractionwas extracted with ethyl acetate
14. dry with materialdried over anhydrous magnesium sulfate
15. filtrationThe mixture was filtered
16. distillationthe solvent in the filtrate was then distilled off under reduced pressure
17. customThe residue was purified by silica gel column chromatography (a mixed solvent of n-heptane and ethyl acetate

ORDレコード

ord-01b4e7d861b04442be3ef13677c0857f

出典データセット

uspto-grants-2013_09

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08530504B2