2-bromo-N-isopropyl-5-nitropyridin-4-amine → 6-bromo-N4-isopropylpyridine-3,4-diamine

HRID 1778024Notes

Reaction equation

HRID 1778024 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([NH:8][CH:9]([CH3:11])[CH3:10])[C:5]([N+:12]([O-])=O)=[CH:4][N:3]=1>CC(O)=O.O.[Fe]>[Br:1][C:2]1[N:3]=[CH:4][C:5]([NH2:12])=[C:6]([NH:8][CH:9]([CH3:11])[CH3:10])[CH:7]=1

Participants

5

Reactant 1

HCID 901766982-bromo-N-isopropyl-5-nitropyridin-4-amine2×

Product 1

HCID 901766496-bromo-N4-isopropylpyridine-3,4-diamine

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

A solution of 2-bromo-N-isopropyl-5-nitropyridin-4-amine (intermediate 258, 4.5 g, 16.61 mmol) in HOAc (59 ml) was added dropwise to a mixture of iron powder (3.75 g, 66.4 mmol) in HOAc (59 ml) at 70° C. After stirring vigorously for 6 h, the reaction mixture was diluted with H2O and extracted with DCM (3×). The combined organic layers were dried over Na2SO4 and evaporated. The crude material was applied to a 80 g RediSep® silica column and purified by normal phase chromatography, eluting with a gradient from 5% to 100% EtOAc/heptanes. Product-containing fractions were combined and evaporated to give the title compound as a brown solid. (UPLC-MS 6) tR 0.56; ESI-MS 230.0/232.0 [M+H]+.

Workup

  1. extractionextracted with DCM (3×)
  2. dry with materialThe combined organic layers were dried over Na2SO4
  3. customevaporated
  4. custompurified by normal phase chromatography
  5. washeluting with a gradient from 5% to 100% EtOAc/heptanes
  6. customevaporated

Sources & evidence

ORD record
ord-befed5b04a81455993f4a17de739687f
Source dataset
uspto-grants-2016_02
Patent number
US09266883B2

Reaction notes

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