Iodine → HCID 15239211, compound

Temperature

-7 °C

The general procedure of Krebs, Aust. J. Chem., 42, 1291 (1989), was employed. Ethyl 3-amino-4,4,4-trifluorocrotonate (9.16 g (gram), 50 mmol (millimole)) was dissolved in 30 mL (milliliter) of N,N-dimethylformamide and 1.2 g of 60 percent in mineral oil sodium hydride (50 mmol) was added in small portions with stirring and cooling to keep the temperature around 25° C. The mixture was stirred for about 1 hr (hour) until the evolution of gas had essentially ceased and was then cooled to -7° C. Carbon disulfide (4.19 g, 55 mmol) in 4 mL of N,N-dimethylformamide was then added slowly with stirring maintaining the temperature below 10° C. by cooling. The mixture was then allowed to warm to 15° C. and 8.29 g (60 mmol) of iodomethane in 4 mL of N,N-dimethylformamide was added with stirring. After 15 min (minutes) the reaction mixture was poured onto 75 g of ice. The red oil that formed was extracted into 2×75 mL of ether. The ethereal solution, dried over sodium sulfate, filtered, and concentrated by evaporation under reduced pressure and the residue was dissolved in 50 mL of ethanol and 7.91 g (100 mmol) of pyridine. A solution prepared by dissolving 12.7 g (50 mmol) of iodine and 20.75 g (125 mmol) of potassium iodide in 100 mL of water was added to this slowly with stirring. The precipitate that formed was collected by filtration and dissolved in ether. The ethereal solution was washed with water and 2×60 mL of 0.5N aqueous sodium thiosulfate solution, dried over sodium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue was recrystallized from hexane to obtain 5.7 g (42 percent of theory) of the title compound as a solid melting at 64°-65° C.

1. temperaturecooling
2. customthe temperature around 25° C
3. stirringThe mixture was stirred for about 1 hr (hour) until the evolution of gas
4. stirringwith stirring
5. temperaturemaintaining the temperature below 10° C.
6. temperatureby cooling
7. temperatureto warm to 15° C.
8. stirringwith stirring
9. customThe red oil that formed
10. extractionwas extracted into 2×75 mL of ether
11. dry with materialThe ethereal solution, dried over sodium sulfate
12. filtrationfiltered
13. concentrationconcentrated by evaporation under reduced pressure
14. dissolutionthe residue was dissolved in 50 mL of ethanol
15. customA solution prepared
16. additionwas added to this slowly
17. stirringwith stirring
18. customThe precipitate that formed
19. filtrationwas collected by filtration
20. dissolutiondissolved in ether
21. washThe ethereal solution was washed with water and 2×60 mL of 0.5N aqueous sodium thiosulfate solution
22. dry with materialdried over sodium sulfate
23. filtrationfiltered
24. concentrationconcentrated by evaporation under reduced pressure
25. customThe residue was recrystallized from hexane

ORD record

ord-e3a1af120fc9472cb3fbb4cad970a3c3

Source dataset

uspto-grants-1994_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05338856