Hydrochloric Acid → 2-(4,4-Difluorobut-3-enylthio)-3-methylisoxazole

温度

0 °C

To a stirred solution of acetone oxime (0.365 g) in dry tetrahydrofuran (20 cm3) at 0° C. under nitrogen was added n-butyl lithium (4.6 cm3 of a 2.5M solution in hexanes) resulting in formation of a pale yellow precipitate. After stirring at 0° C. for 30 minutes, carbon disulfide (0.3 cm3) was added producing a bright orange solution. After a further 10 minutes, 3M HCl (20 cm3) was added and the reaction was heated under reflux for 3 hours and then cooled. The layers were separated and the aqueous layer was extracted with chloroform. The combined organic layers were dried (MgSO4), filtered and evaporated under reduced pressure to give a brown oil. The oil was then taken up in acetone (11 cm3) and 1-bromo-4,4-difluorobut-3-ene (0.77 g) and potassium carbonate (0,87 g) were added and the reaction heated under reflux for 3.5 hours and then cooled. The mixture was then poured into ethyl acetate and 2M HCl and the layers separated. The aqueous layer was extracted with ethyl acetate and the combined organic phases were dried (MgSO4), filtered and evaporated under reduced pressure to give a brown oil. Purification by column chromatography on silica gel using 1:9 ethyl acetate : hexane as eluant gave 2-(4,4-difluorobut-3-enylthio)-3-methylisoxazole (0.105 g). M+ =205; 1H NMR; δ2.30(3H,s); 2.40(2H,m); 3.05(2H,t); 4.25(1H,m); 6.00(1H,s); (oil).

1. customresulting in formation of a pale yellow precipitate
2. customproducing a bright orange solution
3. waitAfter a further 10 minutes
4. temperaturethe reaction was heated
5. temperatureunder reflux for 3 hours
6. temperaturecooled
7. customThe layers were separated
8. extractionthe aqueous layer was extracted with chloroform
9. dry with materialThe combined organic layers were dried (MgSO4)
10. filtrationfiltered
11. customevaporated under reduced pressure
12. customto give a brown oil
13. temperaturethe reaction heated
14. temperatureunder reflux for 3.5 hours
15. temperaturecooled
16. customthe layers separated
17. extractionThe aqueous layer was extracted with ethyl acetate
18. dry with materialthe combined organic phases were dried (MgSO4)
19. filtrationfiltered
20. customevaporated under reduced pressure
21. customto give a brown oil
22. customPurification by column chromatography on silica gel using 1:9 ethyl acetate

ORDレコード

ord-46aed94b4bea4930b53709550344fef5

出典データセット

uspto-grants-1999_09

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05952359