Benzoyl Peroxide → 10,11-Dihydro-10-hydroxy-5H-dibenz[b,f]azepine-5-carbonitrile

HRID 1934792Notes

Reaction equation

HRID 1934792 reaction equation
[C:1]([N:3]1[C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=2[CH2:7][CH2:6][C:5]2[CH:14]=[CH:15][CH:16]=[CH:17][C:4]1=2)#[N:2].C(OOC(=O)C1C=CC=CC=1)(=[O:25])C1C=CC=CC=1.C([O-])(O)=O.[Na+]>ClC1C=CC=CC=1.C([O-])(=O)C1C=CC=CC=1.[Cu+2].C([O-])(=O)C1C=CC=CC=1>[C:1]([N:3]1[C:4]2[CH:17]=[CH:16][CH:15]=[CH:14][C:5]=2[CH:6]([OH:25])[CH2:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]1=2)#[N:2]

Participants

6

Reactant 3

HCID 7187Benzoyl PeroxideHCID 516892Sodium BicarbonateHCID 1116033810,11-Dihydro-5H-dibenzo[b,f]azepine-5-carbonitrile

Product 1

HCID 994277310,11-Dihydro-10-hydroxy-5H-dibenz[b,f]azepine-5-carbonitrileYield 45%

Reagents, catalysts & solvents 2

HCID 164650Cupric benzoateCatalystHCID 7964ChlorobenzeneSolvent

Conditions

Temperature
50 °C

Procedure

6.60 g (0.030 mols) of (I) are dissolved in 45 ml of chlorobenzene, heating to 50° C. under stirring, then added with 0.82 g (0.003 mols) of copper(II) benzoate and 6.9 g (0.033 mols) of dibenzoylperoxide. The reaction mixture is heated to 90° C. and stirred for 3 hours, then cooled to 40° C., added with 40 ml of a 3% HCI solution and stirred at 40° C. for 30 minutes, then at 80° C. for 5 hours. 20 ml of a NaHCO3 saturated solution are added to the mixture, which is stirred for 30 minutes and decanted for 1 hour The aqueous phase is separated and re-extracted with 8 ml of chlorobenzene. The combined organic phases are washed with water (10 ml), dried and concentrated at 60° C. to 20 ml, and 20 ml of hexane are added at this temperature. The mixture is cooled to 0-5° C. for 30 minutes and the solid is filtered to obtain 3.16 g (45%) of compound (VI), m.p. 112-3° C., with good purity.

Workup

  1. temperatureThe reaction mixture is heated to 90° C.
  2. stirringstirred for 3 hours
  3. temperaturecooled to 40° C.
  4. additionadded with 40 ml of a 3% HCI solution
  5. stirringstirred at 40° C. for 30 minutes
  6. stirringis stirred for 30 minutes
  7. customdecanted for 1 hour The aqueous phase
  8. customis separated
  9. extractionre-extracted with 8 ml of chlorobenzene
  10. washThe combined organic phases are washed with water (10 ml)
  11. customdried
  12. concentrationconcentrated at 60° C. to 20 ml, and 20 ml of hexane
  13. additionare added at this temperature
  14. temperatureThe mixture is cooled to 0-5° C. for 30 minutes
  15. filtrationthe solid is filtered

Sources & evidence

ORD record
ord-da5aac667520485d8f3c4418768cf4ca
Source dataset
uspto-grants-2002_05
Patent number
US06384217B1

Reaction notes

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