Ammonium Chloride → (R)-5,5'-(1,4-dimethyl-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepine-6,8(5H)-diyl)dipyridin-2-amine

HRID 1485452Notes

Reaction equation

HRID 1485452 reaction equation
[CH3:1][C:2]1[N:6]2[C:7]3[CH:25]=[CH:24][C:23]([C:26]4[CH:27]=[CH:28][C:29]([NH2:32])=[N:30][CH:31]=4)=[CH:22][C:8]=3[N:9]([C:13]3[CH:14]=[N:15][C:16]([N+:19]([O-])=O)=[CH:17][CH:18]=3)[CH2:10][C@@H:11]([CH3:12])[C:5]2=[N:4][N:3]=1.[Cl-].[NH4+]>[Fe].C(O)C>[CH3:1][C:2]1[N:6]2[C:7]3[CH:25]=[CH:24][C:23]([C:26]4[CH:27]=[CH:28][C:29]([NH2:32])=[N:30][CH:31]=4)=[CH:22][C:8]=3[N:9]([C:13]3[CH:18]=[CH:17][C:16]([NH2:19])=[N:15][CH:14]=3)[CH2:10][C@@H:11]([CH3:12])[C:5]2=[N:4][N:3]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 70979691(R)-5-(1,4-dimethyl-6-(6-nitropyridin-3-yl)-5,6-dihydro-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepin-8-yl)pyridin-2-amine

Product 1

HCID 70979891(R)-5,5'-(1,4-dimethyl-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepine-6,8(5H)-diyl)dipyridin-2-amineYield 20%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

Iron powder (56 mg, 1 mmol) was added to a mixture of (R)-5-(1,4-dimethyl-6-(6-nitropyridin-3-yl)-5,6-dihydro-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepin-8-yl)pyridin-2-amine (86 mg, 0.2 mmol) in a mixed solvents of ammonium chloride aqueous (2 mL) and ethanol (10 mL). Once addition was complete, the mixture was heated to 60° C. for 2 hours. The mixture was filtered. The filtrate was concentrated, diluted with water (10 mL), extracted with ethyl acetate (20 mL×2). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give a residue which was purified by column chromatography (silica gel, dichloromethane/methanol=8:1) to afford (R)-5,5′-(1,4-dimethyl-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepine-6,8(5H)-diyl)dipyridin-2-amine (8 mg, 20%).

Workup

  1. additionOnce addition
  2. filtrationThe mixture was filtered
  3. concentrationThe filtrate was concentrated
  4. additiondiluted with water (10 mL)
  5. extractionextracted with ethyl acetate (20 mL×2)
  6. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give a residue which
  10. customwas purified by column chromatography (silica gel, dichloromethane/methanol=8:1)

Sources & evidence

ORD record
ord-9dff0f332d4344a0a63a131f421789e5
Source dataset
uspto-grants-2016_08
Patent number
US09422292B2

Reaction notes

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