4,9-Dibromo-6-(4-methyl-1-piperazinyl)-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]-benzodiazepine → 4,9-Dibromo-6-(4-methyl-1-piperazinyl)benzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine

HRID 35137Notes

Reaction equation

HRID 35137 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:26]=1)[C:7]([N:19]1[CH2:24][CH2:23][N:22]([CH3:25])[CH2:21][CH2:20]1)=[N:8][C:9]1[CH:17]=[C:16]([Br:18])[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:26]=1)[C:7]([N:19]1[CH2:20][CH2:21][N:22]([CH3:25])[CH2:23][CH2:24]1)=[N:8][C:9]1[CH:17]=[C:16]([Br:18])[CH:15]=[CH:14][C:10]=13

Participants

4

Reactant 1

HCID 138233094,9-Dibromo-6-(4-methyl-1-piperazinyl)-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]-benzodiazepine

Product 1

HCID 104125944,9-Dibromo-6-(4-methyl-1-piperazinyl)benzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepineYield 75.2%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalyst2×HCID 6212ChloroformSolvent

Procedure

A mixture 4,9-dibromo-6-(4-methyl-1-piperazinyl)-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]-benzodiazepine (4.5 g, 9.45 mmoles) and manganese(IV) dioxide (7.0 g) in chloroform (150 ml) was heated under reflux for 3.5 hours. An additional 4.5 g of manganese dioxide was added. The reaction mixture was stirred overnight at room temperature. The mixture was filtered through celite and the filtrate was concentrated. The residue was purified by flash chromatography over a silica gel column (140 gm), eluted with 2% methanol:98% dichloromethane (2 l). The appropriate fractions were collected and evaporated. Crystallization of the residue from isopropanol (10 ml) yielded 3.37 g (75%) of product, mp 158°-159° C.

Workup

  1. temperatureunder reflux for 3.5 hours
  2. filtrationThe mixture was filtered through celite
  3. concentrationthe filtrate was concentrated
  4. customThe residue was purified by flash chromatography over a silica gel column (140 gm)
  5. washeluted with 2% methanol
  6. customThe appropriate fractions were collected
  7. customevaporated
  8. customCrystallization of the residue from isopropanol (10 ml)

Sources & evidence

ORD record
ord-4cb78f0453c745de940293672f43885b
Source dataset
uspto-grants-1988_08
Patent number
US04764616

Reaction notes

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