Ammonium Chloride → HCID 21106349, compound

HRID 855939Notes

Reaction equation

HRID 855939 reaction equation
[I:1][C:2]1[CH:3]=[C:4]([N+:11]([O-])=O)[CH:5]=[C:6]2[C:10]=1[NH:9][CH:8]=[CH:7]2.[Cl-:14].[NH4+]>CO.O.[Fe]>[ClH:14].[I:1][C:2]1[CH:3]=[C:4]([NH2:11])[CH:5]=[C:6]2[C:10]=1[NH:9][CH:8]=[CH:7]2

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 21106351HCID 21106351, compound

Product 1

HCID 21106349HCID 21106349, compoundYield 120.8%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

A solution of 7-iodo-5-nitro-1H-indole III (20 g, 69.4 mmol) in methanol (650 mL) at 25° C. was treated with a solution of ammonium chloride (26.1 g, 485.8 mmol) in water (550 mL) and iron powder (13.6 g, 242.9 mmol). The mixture was heated to 100° C. under a nitrogen atmosphere for 5 h. The resulting mixture was filtered through a pad of celite and the celite pad washed with hot methanol. The filtrate was concentrated in vacuo and the residue was partitioned between methylene chloride and water and separated. The pH of the aqueous layer was adjusted to pH=10 with ammonium hydroxide and extracted with methylene chloride. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to a volume of 250 mL. This solution was treated with a 4.0M aqueous hydrochloric acid solution in dioxane and stirred at 25° C. for 2 h. The precipitate was collected by filtration and washed with methylene chloride and petroleum ether to afford 7-iodo-1H-indol-5-ylamine hydrochloride IV (24.7 g, quant.) as a gray solid: 1H NMR (DMSO-d6, 300 MHz) δ 11.34 (broad s, 1H), 9.93 (broad s, 2H), 7.56 (d, J=1.46 Hz, 1H), 7.48 (t, J=2.74 Hz, 1H), 7.44 (d, J=1.83 Hz, 1H), 6.68 (dd, J1=1.83 Hz, J2=2.93 Hz, 1H).

Workup

  1. filtrationThe resulting mixture was filtered through a pad of celite
  2. washthe celite pad washed with hot methanol
  3. concentrationThe filtrate was concentrated in vacuo
  4. customthe residue was partitioned between methylene chloride and water
  5. customseparated
  6. extractionextracted with methylene chloride
  7. dry with materialThe combined organic layers were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo to a volume of 250 mL
  10. additionThis solution was treated with a 4.0M aqueous hydrochloric acid solution in dioxane
  11. filtrationThe precipitate was collected by filtration
  12. washwashed with methylene chloride and petroleum ether

Sources & evidence

ORD record
ord-9601a3b8d4f647febbf347896ca7ac39
Source dataset
uspto-grants-2007_08
Patent number
US07262297B2

Reaction notes

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