4-Bromo-6-(4-methyl-1-piperazinyl)-1,2dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine → 4-Bromo-6-(4-methyl-1-piperazinyl)benzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine

HRID 35116Notes

Reaction equation

HRID 35116 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[CH2:13][CH2:12][N:11]3[C:5]2=[C:6]([CH:25]=1)[C:7]([N:18]1[CH2:23][CH2:22][N:21]([CH3:24])[CH2:20][CH2:19]1)=[N:8][C:9]1[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=13>C(Cl)(Cl)Cl.[O-2].[O-2].[Mn+4]>[Br:1][C:2]1[CH:3]=[C:4]2[CH:13]=[CH:12][N:11]3[C:5]2=[C:6]([CH:25]=1)[C:7]([N:18]1[CH2:23][CH2:22][N:21]([CH3:24])[CH2:20][CH2:19]1)=[N:8][C:9]1[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=13

Participants

4

Reactant 1

HCID 138232944-Bromo-6-(4-methyl-1-piperazinyl)-1,2dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine

Product 1

HCID 138233004-Bromo-6-(4-methyl-1-piperazinyl)benzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepineYield 65.5%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalyst2×HCID 6212ChloroformSolvent

Procedure

To a solution of 4-bromo-6-(4-methyl-1-piperazinyl)-1,2dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine (5.7 g, 14.3 mmoles) in chloroform (100 ml) was added manganese dioxide (5 g) and the mixture was heated at gentle reflux for 24 hours. Additional manganese dioxide was added and reflux was continued for 36 hours. The mixture was filtered and the solids were washed with dichloromethane. The filtrate was concentrated at reduced pressure. The residue was purified on a silica gel column (160 g), eluted with a mixture of methanol and dichloromethane (1.5% methanol in dichloromethane, 4 l, 2% methanol in dichloromethane, 2 l). The fractions containing pure product were combined and concentrated to give 3.7 g (64%) of product. Recrystallization from toluene (23 ml) yielded the analytical sample, mp 157°-159° C.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat gentle reflux for 24 hours
  3. temperaturereflux
  4. filtrationThe mixture was filtered
  5. washthe solids were washed with dichloromethane
  6. concentrationThe filtrate was concentrated at reduced pressure
  7. customThe residue was purified on a silica gel column (160 g)
  8. washeluted with a mixture of methanol and dichloromethane (1.5% methanol in dichloromethane, 4 l, 2% methanol in dichloromethane, 2 l)
  9. additionThe fractions containing pure product
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-ecb5cd67fa8e42909950438c3cd30787
Source dataset
uspto-grants-1988_08
Patent number
US04764616

Reaction notes

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