Methylamine → 1-(5-Fluoro-2-(methylamino)phenyl)ethanone

HRID 358676

반응식

HRID 358676 반응식
F[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[C:9](=[O:11])[CH3:10].[CH3:12][NH2:13].[OH-].[Na+]>[Cu].Cl>[F:8][C:5]1[CH:6]=[CH:7][C:2]([NH:13][CH3:12])=[C:3]([C:9](=[O:11])[CH3:10])[CH:4]=1

참가 물질

6

반응물 3

HCID 6329MethylamineHCID 14798Sodium HydroxideHCID 747941-(2,5-Difluorophenyl)ethan-1-one

생성물 1

HCID 450864161-(5-Fluoro-2-(methylamino)phenyl)ethanone

시약·촉매·용매 2

HCID 23978Copper촉매HCID 313Hydrochloric Acid용매

실험 절차

A mixture of 2',5'-difluoroacetophenone (20 g), methylamine (33% w/w solution in industrial methylated spirit, 31ml), industrial methylated spirit (30 ml) and copper powder (0.2 g) was heated at 80° in a sealed pressure vessel for 24 hours. The reaction mixture was allowed to cool to ambient temperature and the mixture washed out of the vessel with industrial methylated spirit (2×30 ml). A solution of sodium sulphide nonahydrate (1 g) in water (10 ml) was added to the combined reaction mixture and washings and the mixture heated to 50° for 15 minutes. The mixture was filtered through diatomaceous earth (sold under the trade name CELITE) and the filter bed washed with industrial methylated spirit (50 ml). The combined filtrate and washings were evaporated to give an oil which was stirred with hydrochloric acid (5M, 80 ml) overnight. The mixture was adjusted to pH 8-9 using aqueous sodium hydroxide (specific gravity 1.5) and then extracted with dichloromethane (3×100 ml). The combined extracts were dried over magnesium sulphate and the solvent removed by distillation. The residue was extracted with diethyl ether (100 ml), the extract treated with activated charcoal (5 g) and the solvent removed by distillation. The residue was purified by flash chromatography on a silica gel column eluted with dichloromethane:petroleum ether (1:1) to give the novel compound 5'-fluoro-2'-(methylamino)acetophenone, m.p. 43°-45°.

후처리

  1. temperaturewas heated at 80° in a sealed pressure vessel for 24 hours
  2. washthe mixture washed out of the vessel with industrial methylated spirit (2×30 ml)
  3. additionA solution of sodium sulphide nonahydrate (1 g) in water (10 ml) was added to the combined reaction mixture and washings
  4. temperaturethe mixture heated to 50° for 15 minutes
  5. filtrationThe mixture was filtered through diatomaceous earth (
  6. washwashed with industrial methylated spirit (50 ml)
  7. customThe combined filtrate and washings were evaporated
  8. customto give an oil which
  9. extractionextracted with dichloromethane (3×100 ml)
  10. dry with materialThe combined extracts were dried over magnesium sulphate
  11. customthe solvent removed by distillation
  12. extractionThe residue was extracted with diethyl ether (100 ml)
  13. additionthe extract treated with activated charcoal (5 g)
  14. customthe solvent removed by distillation
  15. customThe residue was purified by flash chromatography on a silica gel column
  16. washeluted with dichloromethane:petroleum ether (1:1)

출처 및 근거

ORD 기록
ord-7e549fd6b84e4215b557aedba5db22ba
출처 데이터셋
uspto-grants-1991_03
특허 번호
US04997840

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