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

HRID 2036664Notes

Reaction equation

HRID 2036664 reaction equation
[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

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

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)]−.

Workup

  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

Sources & evidence

ORD record
ord-da7c9fd3414c4bc1b683cb67eecf507d
Source dataset
uspto-grants-2013_11
Patent number
US08575183B2

Reaction notes

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