Sodium Hydroxide → 9-Bromo-6-(4-phenylmethyl-1-piperazinyl)-1,2-dihydrobenzo[b]-pyrrolo[3,2,1-jk][1,4]benzodiazepine

HRID 4010Notes

Reaction equation

HRID 4010 reaction equation
[Br:1][C:2]1[CH:19]=[CH:18][C:5]2[N:6]3[CH2:17][CH2:16][C:15]4[C:7]3=[C:8]([CH:12]=[CH:13][CH:14]=4)[C:9](=O)[NH:10][C:4]=2[CH:3]=1.[CH2:20]([N:27]1[CH2:32][CH2:31][NH:30][CH2:29][CH2:28]1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[OH-].[Na+]>[Ti](Cl)(Cl)(Cl)Cl.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:19]=[CH:18][C:5]2[N:6]3[CH2:17][CH2:16][C:15]4[C:7]3=[C:8]([CH:12]=[CH:13][CH:14]=4)[C:9]([N:30]3[CH2:31][CH2:32][N:27]([CH2:20][C:21]4[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=4)[CH2:28][CH2:29]3)=[N:10][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 759941-BenzylpiperazineHCID 138232839-Bromo-1,2dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine-6-one

Product 1

HCID 138232979-Bromo-6-(4-phenylmethyl-1-piperazinyl)-1,2-dihydrobenzo[b]-pyrrolo[3,2,1-jk][1,4]benzodiazepine

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 1140TolueneSolvent

Procedure

A stirred mixture of 7.88 g (0.0250 mole) of 9-bromo-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine-6-one and 1200 ml of toluene was heated under nitrogen until a solution resulted. Then there was added 44.1 g (0.250 mole) of N-benzylpiperazine, followed by 14.2 g (0.0750 mole) of titanium tetrachloride. The mixture was heated under reflux for 3 hours, cooled to room temperature and treated with 500 ml of 2N sodium hydroxide. After stirring vigorously for 15 minutes, the layers were separated. The aqueous phase was extracted further with 300 ml of toluene. The toluene layers were combined, washed once with 2N sodium hydroxide solution, twice with water, dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was taken up in 50 ml of hot methanol, from which 7.00 g (59%) of product crystallized. Recrystallization from a solution of dichloromethane (10 ml) to which methanol (50 ml) was added afforded the analytical sample, mp 129°-131° C.

Workup

  1. temperaturewas heated under nitrogen until a solution
  2. customresulted
  3. temperatureThe mixture was heated
  4. temperatureunder reflux for 3 hours
  5. customthe layers were separated
  6. extractionThe aqueous phase was extracted further with 300 ml of toluene
  7. washwashed once with 2N sodium hydroxide solution, twice with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customcrystallized
  11. customRecrystallization from a solution of dichloromethane (10 ml) to which methanol (50 ml)
  12. additionwas added
  13. customafforded the analytical sample, mp 129°-131° C.

Sources & evidence

ORD record
ord-480f4ab5898942408e785b504ff992e5
Source dataset
uspto-grants-1988_02
Patent number
US04723007

Reaction notes

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