Dimethylformamide → 5-nitro-1H-indol-1-amine

HRID 2382108Notes

Reaction equation

HRID 2382108 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:7]=[C:8]2[C:12](=[CH:13][CH:14]=1)[NH:11][CH:10]=[CH:9]2)([O-:5])=[O:4].C[N:16](C=O)C>>[N+:3]([C:6]1[CH:7]=[C:8]2[C:12](=[CH:13][CH:14]=1)[N:11]([NH2:16])[CH:10]=[CH:9]2)([O-:5])=[O:4]

Participants

4

Reactant 3

HCID 6228DimethylformamideHCID 225235-NitroindoleHCID 24758Sodium hydride

Product 1

HCID 105834305-nitro-1H-indol-1-amineYield 97%

Conditions

Temperature
0 °C

Procedure

NaH (60%, 421.5 mmol) is added portion-wise to a solution of 5-nitro-1H-indole (28.1 mmol) in anhydrous DMF (80 mL) at 0° C. and the mixture is stirred at 0° C. under N2 for 10 min. HOSA (140.5 mmol) is added portion-wise for 30 minutes and the mixture is stirred at 0° C. for 2 h. The reaction is quenched with water. Additional water (250 mL) is added and the mixture is extracted with EtOAc (3×100 mL). The combined organic layer is washed with water (2×30 mL), brine (30 mL), dried (Na2SO4), filtered and concentrated. The residue is washed with heptane (2×20 mL) and recrystallized from EtOAc to afford 5-nitro-indole-1-ylamine (4.84 g, 97%) as a solid. MS: 178 (M+H); 1H NMR (300 MHz, CDCl3): δ 4.93(br, 2N—H), 6.62(d, H), 7.30(d, H), 7.52(d, H), 8.17(d, H), 8.58 (s, H).

Workup

  1. additionHOSA (140.5 mmol) is added portion-wise for 30 minutes
  2. stirringthe mixture is stirred at 0° C. for 2 h
  3. customThe reaction is quenched with water
  4. additionAdditional water (250 mL) is added
  5. extractionthe mixture is extracted with EtOAc (3×100 mL)
  6. washThe combined organic layer is washed with water (2×30 mL), brine (30 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. washThe residue is washed with heptane (2×20 mL)
  11. customrecrystallized from EtOAc

Sources & evidence

ORD record
ord-241708c548b546ac9a46c73bbba1d1ab
Source dataset
uspto-grants-2012_09
Patent number
US08258130B2

Reaction notes

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