Methyl 5-nitroisoquinoline-3-carboxylate → Methyl 5-aminoisoquinoline-3-carboxylate

HRID 887202

Reaction equation

HRID 887202 reaction equation
[N+:1]([C:4]1[CH:13]=[CH:12][CH:11]=[C:10]2[C:5]=1[CH:6]=[C:7]([C:14]([O:16][CH3:17])=[O:15])[N:8]=[CH:9]2)([O-])=O>C(O)(=O)C.O.[Fe]>[NH2:1][C:4]1[CH:13]=[CH:12][CH:11]=[C:10]2[C:5]=1[CH:6]=[C:7]([C:14]([O:16][CH3:17])=[O:15])[N:8]=[CH:9]2

Participants

4

Reactant 1

HCID 22032663Methyl 5-nitroisoquinoline-3-carboxylate

Product 1

HCID 22032628Methyl 5-aminoisoquinoline-3-carboxylate

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 21899381Acetic acid--water (1/1)Solvent

Procedure

The product of Example 71A (10.33 g, 44.5 mmol) in acetic acid/water (3/1) (320 mL) was treated with iron powder (5.06 g, 90.7 mmol). After stirring for 16 hours at room temperature, the reaction mixture was filtered the filtrate concentrated under reduced pressure to approximately half the original volume. The mixture was then extracted with dichloromethane (3×200 mL). The organic fractions were combined, dried (MgSO4), and the filtrate concentrated under reduced pressure to afford crude material. A precipitate formed in the aqueous phase after sitting for several hours. This was filtered to afford additional crude material. The crude material was purified by column chromatography (2% methanol/CH2Cl2) to provide the title compound. MS (ESI+) m/z 203 (M+H)+; MS (ESI−) m/z 201 (M−H)−; 1H NMR (DMSO-d6, 300 MHz) δ 3.92 (s, 3H), 6.34 (s, 2H), 6.96 (dd, J 1.0, 7.8, 1H), 7.31 (d, J 8.1, 1H), 7.51 (t, J 7.9, 1H), 8.82 (s, 1H), 9.15 (s, 1H); Anal. Calcd for C11H10N2O2: C, 65.34; H, 4.99; N, 13.85. Found: C, 65.03; H, 4.95; N, 13.65.

Workup

  1. filtrationthe reaction mixture was filtered the filtrate
  2. concentrationconcentrated under reduced pressure to approximately half the original volume
  3. extractionThe mixture was then extracted with dichloromethane (3×200 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationthe filtrate concentrated under reduced pressure
  6. customto afford crude material
  7. customA precipitate formed in the aqueous phase
  8. waitafter sitting for several hours
  9. filtrationThis was filtered
  10. customto afford additional crude material
  11. customThe crude material was purified by column chromatography (2% methanol/CH2Cl2)

Sources & evidence

ORD record
ord-23f016115cad4709a33eee481cc63414
Source dataset
uspto-grants-2012_08
Patent number
US08247413B2

Linked notes

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