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Methanol → 9Chloro-6,11-dihydro-5H-dibenz[b,e]azepine

HRID 1288918
Notes
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Reaction equation

HRID 1288918 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=O)[NH:10][C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[C:7](=O)[C:6]=2[CH:18]=1.[B].CSC.CO>O1CCCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][NH:10][C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[CH2:7][C:6]=2[CH:18]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 887MethanolHCID 9833925Boron, trihydro(thiobis(methane))-, (T-4)-HCID 540117039-Chloro-5H-dibenz[b,e]azepin-6,11-dione

Product 1

HCID 541749289Chloro-6,11-dihydro-5H-dibenz[b,e]azepineYield 64.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a mixture of 7.28 g of 9-chloro-5H-dibenz[b,e]azepin-6,11-dione in 25 ml of tetrahydrofuran under argon is added 8.5 ml of 10 molar boron-dimethylsulfide in tetrahydrofuran. The mixture is stirred 18 hours at room temperature, 30 ml of tetrahydrofuran added and the mixture refluxed for 3 hours (solids dissolved). The solution is cooled to room temperature and 25 ml of methanol added dropwise. The volatiles are removed under vacuum. To the residue is added 100 ml of 2N NaOH. The mixture is refluxed overnight and filtered. The solid is extracted with dichloromethane and the extract is washed with 2N citric acid, water and dried (Na2SO4). The solvent is removed to give 4.2 g of solid which is triturated with ethyl acetate-hexane (1:2) to give crystals, m.p. 137° C. to 141° C.

Workup

  1. temperaturethe mixture refluxed for 3 hours
  2. dissolution(solids dissolved)
  3. temperatureThe solution is cooled to room temperature
  4. customThe volatiles are removed under vacuum
  5. additionTo the residue is added 100 ml of 2N NaOH
  6. temperatureThe mixture is refluxed overnight
  7. filtrationfiltered
  8. extractionThe solid is extracted with dichloromethane
  9. washthe extract is washed with 2N citric acid, water
  10. dry with materialdried (Na2SO4)
  11. customThe solvent is removed

Sources & evidence

ORD record
ord-116d2562404e41138409473e1642077a
Source dataset
uspto-grants-1998_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05747487

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes