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Hydrochloric Acid → Methyl(3-methylaminobenzyl)sulfone

HRID 1017231
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HRID 1017231 반응식
[C:1](OC(=O)C)(=O)C.[CH3:8][S:9]([CH2:12][C:13]1[CH:14]=[C:15]([NH2:19])[CH:16]=[CH:17][CH:18]=1)(=[O:11])=[O:10].Cl.[OH-].[Na+]>O1CCCC1.O.CO.C(O)=O>[CH3:8][S:9]([CH2:12][C:13]1[CH:14]=[C:15]([NH:19][CH3:1])[CH:16]=[CH:17][CH:18]=1)(=[O:10])=[O:11]
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참가 물질

9

반응물 4

HCID 313Hydrochloric AcidHCID 7918Acetic AnhydrideHCID 14798Sodium HydroxideHCID 219563393-(Methanesulfonylmethyl)aniline

생성물 1

HCID 17908539Methyl(3-methylaminobenzyl)sulfone

시약·촉매·용매 4

HCID 284Formic Acid용매
HCID 887
Methanol
용매
HCID 962Water용매
HCID 8028Tetrahydrofuran용매3회

반응 조건

온도
50 °C

실험 절차

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.

후처리

  1. customthe solution obtained
  2. customto return to room temperature
  3. temperatureis cooled to −20° C
  4. temperatureis maintained
  5. stirringAfter stirring for 2 hours at −20° C.
  6. waitfor 48 hours at 20° C.
  7. filtrationthe mixture is filtered
  8. washwashed with three times 50 cm3 of diisopropyl ether
  9. customdried under reduced pressure (2.7 kPa)
  10. customA solid A is obtained
  11. concentrationThe filtrate is concentrated to half the volume
  12. filtrationthe resulting suspension is filtered
  13. washwashed with diisopropyl ether
  14. customdried
  15. customA solid B is obtained
  16. temperaturethe mixture, cooled to 0° C.
  17. temperatureheated
  18. temperatureat reflux temperature for 3 hours
  19. temperatureThe reaction mixture, cooled to +5° C.
  20. stirringstirred for 1 hour at room temperature
  21. temperatureThe mixture is heated
  22. temperatureunder reflux for one hour
  23. extractionThe resulting mixture is extracted with 500 cm3 of ethyl acetate
  24. washthe organic phase is washed successively with a saturated aqueous sodium hydrogen carbonate solution
  25. dry with materialwith brine, and is then dried over magnesium sulfate
  26. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  27. customthe solution obtained
  28. washis washed with 100 cm3 of ethyl acetate
  29. extractionis then extracted with twice 75 cm3 of ethyl acetate
  30. dry with materialThe combined extracts are dried over magnesium sulfate
  31. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)

출처 및 근거

ORD 기록
ord-8ec9a8a8221d4aa8b1cf101534c79380
출처 데이터셋
uspto-grants-2002_11
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06479479B2

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