Chloral → HCID 20154666, compound

Temperature

0 °C

44.10 g (0.4 mole) of cyclooctene and 58.95 g (0.4 mole) of chloral in 60 ml of petroleum ether were initially taken in a 2-necked flask equipped with a magnetic stirrer, an internal thermometer and a drying tube. The mixture was cooled to ≤0° C. by means of a cold bath. 5.5 g (0.04 mole) of aluminum trichloride were added a little at a time in the course of 15 minutes, the temperature being kept at 0° C. Stirring was continued for a further 4 hours at this temperature, after which the mixture was left to stand for 15 hours at room temperature. For hydrolysis, the mixture was cooled to 0° C., and an equal volume of ice water was slowly added. The dark brown petroleum ether phase was separated off, filtered to remove the insoluble polymers and washed three times with saturated aqueous sodium chloride solution. The organic phase was dried over magnesium sulfate and evaporated down in a rotary evaporator. The crude product was purified by fractional distillation under reduced pressure (105°-118° C.; 0.5 mm Hg). 78 g (0.3 mole; 75% by weight) of a mixture of two compounds in a ratio of 1:1 were obtained. The two compounds were separated by liquid chromatography over a silica gel column (diameter 5 cm, length 20 cm) using a 1:1 cyclohexane/methylene chloride mixture as the mobile phase. In addition to 3-(1'-hydroxy-2',2',2'-trichloroethyl)-1-cyclooctene, a compound of the probable structure 8-trichloromethyl-7-oxabicyclo[4.2.2]decane, of the formula ##STR37## was isolated.

1. customequipped with a magnetic stirrer
2. temperatureThe mixture was cooled to ≤0° C. by means of a cold bath
3. custombeing kept at 0° C
4. waitafter which the mixture was left
5. waitto stand for 15 hours at room temperature
6. customFor hydrolysis
7. customThe dark brown petroleum ether phase was separated off
8. filtrationfiltered
9. customto remove the insoluble polymers
10. washwashed three times with saturated aqueous sodium chloride solution
11. dry with materialThe organic phase was dried over magnesium sulfate
12. customevaporated down in a rotary evaporator
13. distillationThe crude product was purified by fractional distillation under reduced pressure (105°-118° C.; 0.5 mm Hg)
14. addition78 g (0.3 mole; 75% by weight) of a mixture of two compounds in a ratio of 1:1
15. customwere obtained
16. customThe two compounds were separated by liquid chromatography over a silica gel column (diameter 5 cm, length 20 cm)
17. additionIn addition to 3-(1'-hydroxy-2',2',2'-trichloroethyl)-1-cyclooctene

ORD record

ord-f66740c9c8b44ba485b73dd663306941

Source dataset

uspto-grants-1987_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04681977