Azobisisobutyronitrile → Ethyl 2-(bromomethyl)-3,6-dichlorobenzoate

HRID 577498Notes

Reaction equation

HRID 577498 reaction equation
[Cl:1][C:2]1[C:3]([CH3:14])=[C:4]([C:10]([Cl:13])=[CH:11][CH:12]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:15]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)Cl.ClCCl>[Br:15][CH2:14][C:3]1[C:2]([Cl:1])=[CH:12][CH:11]=[C:10]([Cl:13])[C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

6

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 86723723Ethyl 3,6-dichloro-2-methylbenzoate

Product 1

HCID 86723724Ethyl 2-(bromomethyl)-3,6-dichlorobenzoateYield 100%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 3,6-dichloro-2-methylbenzoate (253b, 120 g, 0.52 mol) and N-bromosuccinimide (147 g, 0.82 mol) in chloroform (1 L) was treated with azobisisobutyronitrile (25.3 g, 0.15 mol) and the mixture refluxed overnight. After cooling to room temperature, the mixture was diluted with dichloromethane (800 mL) and washed with water (1.2 L). The aqueous layer was extracted with dichloromethane (800 mL). The combined organic extracts were washed with saturated aqueous sodium chloride solution (1.5 L), dried over sodium sulfate, and concentrated in vacuo to give ethyl 2-(bromomethyl)-3,6-dichlorobenzoate (253c, 160 g, 100% yield) which was used without further purification.

Workup

  1. temperaturethe mixture refluxed overnight
  2. washwashed with water (1.2 L)
  3. extractionThe aqueous layer was extracted with dichloromethane (800 mL)
  4. washThe combined organic extracts were washed with saturated aqueous sodium chloride solution (1.5 L)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3d86e46f619942e29e00f8256a694502
Source dataset
uspto-grants-2015_05
Patent number
US09040515B2

Reaction notes

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