Sodium Hydroxide → 6-bromo-N1-(5-fluoropyridin-3-yl)benzene-1,2-diamine

HRID 2036664노트

반응식

HRID 2036664 반응식
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-])=O)[C:3]=1[NH:11][C:12]1[CH:13]=[N:14][CH:15]=[C:16]([F:18])[CH:17]=1.O.O.[Sn](Cl)Cl.[OH-].[Na+]>CCOC(C)=O>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([NH2:8])[C:3]=1[NH:11][C:12]1[CH:13]=[N:14][CH:15]=[C:16]([F:18])[CH:17]=1

참가 물질

5

반응물 3

HCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 58459289N-(2-bromo-6-nitrophenyl)-5-fluoropyridin-3-amine

생성물 1

HCID 584592496-bromo-N1-(5-fluoropyridin-3-yl)benzene-1,2-diamine

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매

실험 절차

A mixture of N-(2-bromo-6-nitrophenyl)-5-fluoropyridin-3-amine (5.686 g, 18.22 mmol) and tin(II) chloride dihydrate (20.56 g, 91 mmol) in EtOAc (121 mL) was heated under reflux with stirring. After 2.5 h, the mixture was cooled to rt. The cooled mixture was poured into 10M aqueous NaOH solution (150 mL). The mixture was extracted with EtOAC (100 mL×2) washed with water (100 mL×2), brine (100 mL×1), dried over Mg2SO4, filtered, and concentrated in vacuo. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a Redi-Sep™ pre-packed silica gel column (120 g), eluting with a gradient of 0% to 30% EtOAc in hexane, to provide 6-bromo-N1-(5-fluoropyridin-3-yl)benzene-1,2-diamine as brown syrupy solid: 1H NMR (400 MHz, DMSO-d6) δ ppm 7.84 (1H, s), 7.76-7.82 (2H, m), 6.91-6.98 (1H, m), 6.81-6.87 (1H, m), 6.77 (1H, dd, J=8.0, 1.4 Hz), 6.39 (1H, dt, J=11.7, 2.3 Hz), 5.28 (2H, s); LC-MS (ESI) m/z 282.0 [M+H (79Br)]+ and 283.9 [M+H (81Br)]−.

후처리

  1. temperaturewas heated
  2. temperatureunder reflux
  3. extractionThe mixture was extracted with EtOAC (100 mL×2)
  4. washwashed with water (100 mL×2), brine (100 mL×1)
  5. dry with materialdried over Mg2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude material was absorbed onto a plug of silica gel
  9. custompurified by chromatography through a Redi-Sep™ pre-packed silica gel column (120 g)
  10. washeluting with a gradient of 0% to 30% EtOAc in hexane

출처 및 근거

ORD 기록
ord-da7c9fd3414c4bc1b683cb67eecf507d
출처 데이터셋
uspto-grants-2013_11
특허 번호
US08575183B2

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