N-bromobutanimide → 12-bromo-2,10-dichloro-12H-5,7-dioxadibenzo[a,d]cyclooctene

HRID 323590Notes

Reaction equation

HRID 323590 reaction equation
[Cl:1][C:2]1[CH:18]=[CH:17][C:5]2[O:6][CH2:7][O:8][C:9]3[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][C:10]=3[CH2:11][C:4]=2[CH:3]=1.[Br:19]N1C(=O)CCC1=O>ClC(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br:19][CH:11]1[C:4]2[CH:3]=[C:2]([Cl:1])[CH:18]=[CH:17][C:5]=2[O:6][CH2:7][O:8][C:9]2[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][C:10]1=2

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 149005562,10-dichloro-12H-dibenzo[d,g][1,3]dioxocine

Product 1

HCID 2272777812-bromo-2,10-dichloro-12H-5,7-dioxadibenzo[a,d]cycloocteneYield 27%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalyst2×HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 2,10-dichloro-12H-dibenzo[d,g][1,3]-dioxocin (21.4 g, 76.1 mmol) and N-bromosuccinimide (13.5 g, 76.1 mmol) in tetrachloromethane (275 mL) was added azobisisobutyronitrile (200 mg, 1.2 mmol). The mixture was heated at 80° C. for 24 h. Another 3×azobisisobutyronitrile (200 mg, 1.2 mmol) was added within the 24 h. The mixture was filtrated and the solution phase concentrated in vacuo. The residue was added dichloromethane (30 mL) and ether (100 mL). The mixture was filtered and the solution phase concentraded in vacuo. The residue was submitted to flash chromatography eluting with heptane/ethyl acetate (3:1) to give 7.4 g (27%) of 12-bromo-2,10-dichloro-12H-5,7-dioxadibenzo[a,d]cyclooctene.

Workup

  1. filtrationThe mixture was filtrated
  2. concentrationthe solution phase concentrated in vacuo
  3. additionThe residue was added dichloromethane (30 mL) and ether (100 mL)
  4. filtrationThe mixture was filtered
  5. washeluting with heptane/ethyl acetate (3:1)

Sources & evidence

ORD record
ord-5fd6e3981ad248989adcf9368136ffe7
Source dataset
uspto-grants-2001_04
Patent number
US06214820B1

Reaction notes

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