反应 #46337

ord-c2314251d3b343369891a1a11bae5b30

反应条件

温度
50°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    其他the solution obtained
  2. 2
    其他to return to room temperature
  3. 3
    温度is cooled to −20° C
  4. 4
    温度is maintained
  5. 5
    workup.STIRRINGAfter stirring for 2 hours at −20° C.
  6. 6
    workup.WAITfor 48 hours at 20° C.
  7. 7
    过滤the mixture is filtered
  8. 8
    洗涤washed with three times 50 cm3 of diisopropyl ether
  9. 9
    其他dried under reduced pressure (2.7 kPa)
  10. 10
    其他A solid A is obtained
  11. 11
    浓缩The filtrate is concentrated to half the volume
  12. 12
    过滤the resulting suspension is filtered
  13. 13
    洗涤washed with diisopropyl ether
  14. 14
    其他dried
  15. 15
    其他A solid B is obtained
  16. 16
    温度the mixture, cooled to 0° C.
  17. 17
    温度heated
  18. 18
    温度at reflux temperature for 3 hours
  19. 19
    温度The reaction mixture, cooled to +5° C.
  20. 20
    workup.STIRRINGstirred for 1 hour at room temperature
  21. 21
    温度The mixture is heated
  22. 22
    温度under reflux for one hour
  23. 23
    萃取The resulting mixture is extracted with 500 cm3 of ethyl acetate
  24. 24
    洗涤the organic phase is washed successively with a saturated aqueous sodium hydrogen carbonate solution
  25. 25
    干燥with brine, and is then dried over magnesium sulfate
  26. 26
    浓缩concentrated to dryness under reduced pressure (2.7 kPa)
  27. 27
    其他the solution obtained
  28. 28
    洗涤is washed with 100 cm3 of ethyl acetate
  29. 29
    萃取is then extracted with twice 75 cm3 of ethyl acetate
  30. 30
    干燥The combined extracts are dried over magnesium sulfate
  31. 31
    浓缩concentrated to dryness under reduced pressure (2.7 kPa)

实验过程

N-[3-(Methylsulfonylmethyl)phenyl]N-methylamine may be obtained by carrying out the procedure in the following manner: a mixture of 9.65 cm3 of formic acid and 19.63 cm3 of acetic anhydride is heated at 50° C. for 3 hours under argon, and then the solution obtained is allowed to return to room temperature. 40 cm3 of tetrahydrofuran are poured in and the medium is cooled to −20° C. After stirring for 2 hours at −20° C., a solution of 14.8 g of 3-(methylsulfonylmethyl)phenylamine is poured in while the temperature is maintained. After stirring for 2 hours at −20° C., and then for 48 hours at 20° C., the mixture is filtered, the solid is drained and then washed with three times 50 cm3 of diisopropyl ether and dried under reduced pressure (2.7 kPa). A solid A is obtained. The filtrate is concentrated to half the volume, the resulting suspension is filtered, the solid is drained, washed with diisopropyl ether and dried. A solid B is obtained. The two solids A and B are combined and taken up in 375 cm3 of tetrahydrofuran and the mixture, cooled to 0° C., is supplemented, over 20 minutes, with 80 cm3 of a 2 M solution of borane-dimethyl sulfide complex in tetrahydrofuran and then heated at reflux temperature for 3 hours. The reaction mixture, cooled to +5° C., is supplemented over 20 minutes with 60 cm3 of methanol, stirred for 1 hour at room temperature and then supplemented with gaseous hydrochloric acid to a pH of 1. The mixture is heated under reflux for one hour and then supplemented with 300 cm3 of water and with a 3 N solution of sodium hydroxide to pH 8. The resulting mixture is extracted with 500 cm3 of ethyl acetate, the organic phase is washed successively with a saturated aqueous sodium hydrogen carbonate solution, and with brine, and is then dried over magnesium sulfate and concentrated to dryness under reduced pressure (2.7 kPa). The residue is taken up in 100 cm3 of 4 N sulfuric acid, the solution obtained is washed with 100 cm3 of ethyl acetate, then alkalinized to pH 8 with 3 N sodium hydroxide and with a saturated aqueous sodium carbonate solution and is then extracted with twice 75 cm3 of ethyl acetate. The combined extracts are dried over magnesium sulfate and concentrated to dryness under reduced pressure (2.7 kPa). 8.98 g of N-[3-(methylsulfonylmethyl)phenyl]N-methylamine are obtained in the form of a pink solid.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US07741316B2uspto-grants-2010_06