Hydrochloric Acid → Benzyl carbamate

To a suspension of 0.85 g (34.6 mmole) magnesium turnings in 25 mL tetrahydrofuran was added 5 mL of a solution of 5 g (28.8 mmole) 1-bromo-4-tert-butylbenzene in 25 mL tetrahydrofuran. One iodine crystal and 1,2-dibromoethane (0.3 mL) was added and the mixture was heated to reflux to initiate the reaction. The rest of the 1-bromo-4-tert-butylbenzene solution was then added dropwise and the reaction mixture was stirred at room temperature for 1 hr. The remaining magnesium was allowed to settle and the supernatant was added in portions to a cooled, previously prepared mixture of 8 g (27.4 mmole) ((S)-1-methyl-2-morpholin-4-yl-2-oxoethyl)-carbamic acid benzyl ester n in 30 mL tetrahydrofuran and 30 mL (60 mmole) 2M isopropylmagnesium chloride in diethyl ether. The reaction mixture was stirred at room temperature for 16 hrs. The mixture was then added to a well-stirred mixture of 100 mL 5% hydrochloric acid and crushed ice. The mixture was extracted with two 50 mL portions ethyl acetate. The organic phase was washed with 25 mL saturated sodium chloride, dried (magnesium sulfate) and concentrated under reduced pressure. (S)-2-(4-tert-Butylphenyl)-1-methyl-2-oxoethyl]-carbamic acid benzyl ester o was isolated as a solid, 9.2 g. m.p. 156-158° C.

1. temperaturethe mixture was heated
2. temperatureto reflux
3. customthe reaction
4. stirringThe reaction mixture was stirred at room temperature for 16 hrs
5. customcrushed ice
6. extractionThe mixture was extracted with two 50 mL portions ethyl acetate
7. washThe organic phase was washed with 25 mL saturated sodium chloride
8. dry with materialdried (magnesium sulfate)
9. concentrationconcentrated under reduced pressure

ORD-Eintrag

ord-202f5758e7c8471b9a3984ff2e02decb

Quelldatensatz

uspto-grants-2003_12

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06667301B2