反应详情

温度

-10 °C

A suspension of methyl N-hydroxycarbamate (17.81 g) in methylene chloride (350 ml) was cooled to about -13° C. (ice/acetone bath), and sequentially treated with 1,3-cyclohexadiene (14.24 g) and a suspension of tetrabutylammonium periodate (84.73 g) in methylene chloride (550 ml). The periodate suspension was added over a one hour period causing the temperature of the reaction to rise to a maximum of -5° C. After the addition of the periodate suspension was complete, the resulting reaction mixture was stirred at about -10° C. for three hours. A 10% sodium bisulfite solution (750 ml) was carefully added to the reaction mixture, while cooling in an ice/acetone bath. After about 45 minutes, the addition of the sodium bisulfite solution was complete. The organic phase was removed, washed with water (2×200 ml) and saturated sodium bicarbonate solution (2×500 ml). The organic phase was dried over sodium chloride, filtered, and concentrated in vacuo to give 180 g of the crude product. A solution of the crude product in methylene chloride was added to silica gel (200 g), and the resulting mixture evaporated to dryness. The title compound was isolated by flash silica-gel filtration, eluting with hexane/ethyl acetate (9:1, 2 L) and hexane/ethyl acetate (7:3, 500 ml). The fractions containing the title compound were combined, dried over sodium chloride and magnesium sulfate, filtered, and concentrated in vacuo to give 27.85 g of an oil. The oil was placed in a freezer to induce crystalization.

1. customthe temperature of the reaction
2. customto rise to a maximum of -5° C
3. customthe resulting reaction mixture
4. temperaturewhile cooling in an ice/acetone bath
5. waitAfter about 45 minutes
6. customThe organic phase was removed
7. washwashed with water (2×200 ml) and saturated sodium bicarbonate solution (2×500 ml)
8. dry with materialThe organic phase was dried over sodium chloride
9. filtrationfiltered
10. concentrationconcentrated in vacuo
11. customto give 180 g of the crude product
12. customthe resulting mixture evaporated to dryness