Ammonium nitrate → 3-Amino-1-phenyl-1,5-dihydrobenzo[b][1,4] diazepine-2,4-dione

HRID 1416111Notes

Reaction equation

HRID 1416111 reaction equation
[NH2:1][CH:2]1[C:8](=[O:9])[N:7](CC2C=CC(OC)=CC=2)[C:6]2[CH:19]=[CH:20][CH:21]=[CH:22][C:5]=2[N:4]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:3]1=[O:29].[N+]([O-])([O-])=O.[NH4+]>C(#N)C.O>[NH2:1][CH:2]1[C:3](=[O:29])[N:4]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:5]2[CH:22]=[CH:21][CH:20]=[CH:19][C:6]=2[NH:7][C:8]1=[O:9]

Participants

4

Reactant 2

HCID 22985Ammonium nitrateHCID 107389603-Amino-1-(4-methoxybenzyI)-5-phenyl-1,5-dihydrobenzo[b][1,4]diazepine-2,4-dione

Product 1

HCID 106832523-Amino-1-phenyl-1,5-dihydrobenzo[b][1,4] diazepine-2,4-dioneYield 87%

Reagents, catalysts & solvents 1

HCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

To a stirred solution of 3-amino-1-(4-methoxybenzyl)-5-phenyl-1,5-dihydrobenzo [b] [1,4] diazepine-2,4-dione (0.50 g) in acetonitrile/H2O (9:1, 12 ml) at ambient temperature was added cerric ammonium nitrate (1.84 g) portionwise over a ten minute period. The solution was stirred overnight at room temperature. The solution was concentrated in vacuo and the resultant solid partitioned between saturated aqueous potassium carbonate (40 ml) and ethanol (60 ml). The phases were separated and the aqueous phase extracted with ethanol (4×50 ml). The ethanol portions were combined, dried over sodium sulfate and concentrated in vacuo to a tan solid. This solid was extracted exhaustively with boiling CH2Cl2 (10×60 ml), the organics combined, dried over sodium sulfate, filtered and concentrated to give the title compound (0.30 g) as a tan solid. 1H (300 MHz, DMSO-d6): d 1.98 (br s, 2H), 4.08 (s, 1H), 6.86 (d, J=8.4 Hz, 1H), 7.11-7.46 (m, 8H), 10.78 (br s, 1H); 13C (75.429 MHz, DMSO-d6): d 56.98, 123.41, 126.22, 126.51, 127.34, 128.30, 128.89, 130.15, 132.29, 134.42, 142.36, 168.13, 169.39. MS (FAB): m/z=268.10 (MH+); TLC (CH2Cl2 /CH3OH,15:1): Rf =0.21

Workup

  1. concentrationThe solution was concentrated in vacuo
  2. customthe resultant solid partitioned between saturated aqueous potassium carbonate (40 ml) and ethanol (60 ml)
  3. customThe phases were separated
  4. extractionthe aqueous phase extracted with ethanol (4×50 ml)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo to a tan solid
  7. extractionThis solid was extracted exhaustively with boiling CH2Cl2 (10×60 ml)
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-6923c4a9d62d4151a815d04c7e0b844e
Source dataset
uspto-grants-1999_06
Patent number
US05910495

Reaction notes

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