Azobisisobutyronitrile → Methyl 6-iodo-5-oxo-5H-dibenzo[a,d]cycloheptene-1-carboxylate

HRID 132998Notes

Reaction equation

HRID 132998 reaction equation
[I:1][C:2]1[C:7]2[C:8](=[O:21])[C:9]3[CH:16]=[CH:15][CH:14]=[C:13]([C:17]([O:19][CH3:20])=[O:18])[C:10]=3[CH2:11][CH2:12][C:6]=2[CH:5]=[CH:4][CH:3]=1.IC1C2C(=O)C3C=CC=CC=3CCC=2C(C(OC)=O)=CC=1.BrN1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[I:1][C:2]1[C:7]2[C:8](=[O:21])[C:9]3[CH:16]=[CH:15][CH:14]=[C:13]([C:17]([O:19][CH3:20])=[O:18])[C:10]=3[CH:11]=[CH:12][C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 58646843Methyl 4-iodo-5-oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-1-carboxylateHCID 58646847methyl 6-iodo-5-oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-1-carboxylate

Product 1

HCID 58646834Methyl 6-iodo-5-oxo-5H-dibenzo[a,d]cycloheptene-1-carboxylate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 260 mg of the mixture of methyl 6-iodo-5-oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-1-carboxylate and its 4-iodo form prepared in Example 6-c in 10 ml carbon tetrachloride were added 130 mg of N-bromosuccinimide and 5 mg of azobisisobutyronitrile, followed by heating under reflux for 2 hours. The reaction mixture was cooled to room temperature and filtered. The filtrate was washed with diethyl ether, and the solvent was removed. To the residue was added 10 ml of dimethylformamide, and further added 0.15 ml of 1,8-diazabicyclo[5.4.0]undecene at room temperature, followed by stirring at room temperature for 10 minutes. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was purified and separated by silica gel column chromatography (ethyl acetate:hexane=1:4), to give 200 mg of a mixture of the title compound with its 4-iodo form as a colorless powder.

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 2 hours
  3. filtrationfiltered
  4. washThe filtrate was washed with diethyl ether
  5. customthe solvent was removed
  6. additionTo the residue was added 10 ml of dimethylformamide, and further added 0.15 ml of 1,8-diazabicyclo[5.4.0]undecene at room temperature
  7. additionWater was added to the reaction mixture
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe organic layer was washed with water
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customthe solvent was evaporated
  12. customThe residue was purified
  13. customseparated by silica gel column chromatography (ethyl acetate:hexane=1:4)

Sources & evidence

ORD record
ord-e847d2b03dcf495ea7f2d037f770c48c
Source dataset
uspto-grants-2008_06
Patent number
US07390797B2

Reaction notes

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