Ammonium Chloride → benzyl (3-(2-amino-1-(6-bromo-1H-indol-3-yl)propyl)-2-methylphenyl)carbamate

HRID 2361401Notes

Reaction equation

HRID 2361401 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6]([CH:11]([C:17]3[C:18]([CH3:34])=[C:19]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[CH:20]=[CH:21][CH:22]=3)[CH:12]([N+:14]([O-])=O)[CH3:13])=[CH:7][NH:8]2)=[CH:4][CH:3]=1.[Cl-].[NH4+]>CO.O1CCCC1.C(OCC)(=O)C.[Zn]>[NH2:14][CH:12]([CH3:13])[CH:11]([C:17]1[C:18]([CH3:34])=[C:19]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH:20]=[CH:21][CH:22]=1)[C:6]1[C:5]2[C:9](=[CH:10][C:2]([Br:1])=[CH:3][CH:4]=2)[NH:8][CH:7]=1

Participants

7

Reactant 2

HCID 25517Ammonium ChlorideHCID 70651981benzyl (3-(1-(6-bromo-1H-indol-3-yl)-2-nitropropyl)-2-methylphenyl)carbamate

Product 1

HCID 70651986benzyl (3-(2-amino-1-(6-bromo-1H-indol-3-yl)propyl)-2-methylphenyl)carbamateYield 95%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of benzyl (3-(1-(6-bromo-1H-indol-3-yl)-2-nitropropyl)-2-methylphenyl)carbamate (4.47 g, 8.56 mmol), ammonium chloride (6.87 g, 128 mmol), and zinc dust (8.40 g, 128 mmol) in methanol (100 mL) and tetrahydrofuran (100 mL) was stirred overnight under nitrogen. The reaction was diluted with ethyl acetate and filtered through a pad of CELITE®. The filtrate was concentrated under reduced pressure, and the residue was diluted with ethyl acetate (150 mL), washed with saturated aqueous sodium bicarbonate (70 mL), and washed with brine (70 mL). The organic layer was collected, and the aqueous layers were sequentially extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to give benzyl (3-(2-amino-1-(6-bromo-1H-indol-3-yl)propyl)-2-methylphenyl)carbamate (4.00 g, 8.12 mmol, 95% yield) as a light brown semi-solid and as a ˜1:1 diastereomers. LC/MS M+1=492.1 and 494.1.

Workup

  1. filtrationfiltered through a pad of CELITE®
  2. concentrationThe filtrate was concentrated under reduced pressure
  3. additionthe residue was diluted with ethyl acetate (150 mL)
  4. washwashed with saturated aqueous sodium bicarbonate (70 mL)
  5. washwashed with brine (70 mL)
  6. customThe organic layer was collected
  7. extractionthe aqueous layers were sequentially extracted with ethyl acetate (2×100 mL)
  8. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a86ebeae2c6e42b98bab8470777bf783
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

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