反应详情

温度

-30 °C

In a 1-liter three-neck flask equipped with a thermometer, a reflex condenser and a calcium chloride tube were placed 350 g of acetonitrile, 70.7 g (0.699 mol) of triethylamine, 33.1 g (0.200 mol) of 2-aminoethyl 2-methylacrylate hydrochloride and 0.2 g of phenothiazine as a polymerization inhibitor, followed by cooling to −30° C. with stirring. After the inside temperature of the flask reached −30° C. C, 36.5 g (0.240 mol) of trifluoromethanesulfonyl fluoride was introduced as a gas into the slurry over 1 hour. Upon completion of the gas introduction, the reaction solution was stirred for 1 hour and then warmed to room temperature. The solvent (acetonitrile) and the unreacted reaction substrate (trifluoromethanesulfonyl fluoride) were evaporated from the reaction solution under a reduced pressure. To the solution was added 1 liter of diisopropyl ether. The resulting slurry was subjected to filtration to filter out precipitates of triethylamine hydrochloride and triethylamine hydrofluoride. The filtrate was washed with 200 ml of 18% aqueous calcium chloride solution and subjected to two-phase separation. The organic phase was further washed three times with 200 g of 10% aqueous sodium chloride solution, and then, dried with 40 g of magnesium sulfate. The magnesium sulfate was removed by filtration. After that, 0.2 g of phenothiazine was added to the organic phase. The solvent was evaporated to obtain 44.2 g of a crude reaction product. The crude reaction product was subjected to distillation under a reduced pressure, thereby yielding 36.0 g of target 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate as an organic fraction at 105-115° C./13Pa. The purity of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate in the organic fraction was determined by gas chromatography to be 97.0%. The organic fraction was dissolved into a mixed solvent of diisopropyl ether and n-hexane under heating. The solution was cooled, thereby collecting 32.4 g of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate as a white crystal. The purity of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate in the crystal was determined by gas chromatography to be 99.0%. The yield of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-me thylacrylate was 61%.

1. customIn a 1-liter three-neck flask equipped with a thermometer, a reflex condenser and a calcium chloride tube
2. customreached −30° C
3. stirringUpon completion of the gas introduction, the reaction solution was stirred for 1 hour
4. temperaturewarmed to room temperature
5. customwere evaporated from the reaction solution under a reduced pressure
6. additionTo the solution was added 1 liter of diisopropyl ether
7. filtrationThe resulting slurry was subjected to filtration
8. filtrationto filter out
9. customprecipitates of triethylamine hydrochloride and triethylamine hydrofluoride
10. washThe filtrate was washed with 200 ml of 18% aqueous calcium chloride solution
11. customsubjected to two-phase separation
12. washThe organic phase was further washed three times with 200 g of 10% aqueous sodium chloride solution
13. dry with materialdried with 40 g of magnesium sulfate
14. customThe magnesium sulfate was removed by filtration
15. additionAfter that, 0.2 g of phenothiazine was added to the organic phase
16. customThe solvent was evaporated
17. customto obtain 44.2 g of a crude
18. customreaction product
19. customThe crude reaction product
20. distillationwas subjected to distillation under a reduced pressure