Acetic Acid → Methyl 4-(Bromomethyl)-2,6-dichloronicotinate

HRID 922052Notes

Reaction equation

HRID 922052 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:6]([Cl:13])=[N:7][C:8]([Cl:12])=[CH:9][C:10]=1[CH3:11])=[O:4].[Br:14]N1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C.C(O)(=O)C>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[C:6]([Cl:13])=[N:7][C:8]([Cl:12])=[CH:9][C:10]=1[CH2:11][Br:14])=[O:4]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 46911843Methyl 2,6-dichloro-4-methylnicotinate

Product 1

HCID 86664328Methyl 4-(Bromomethyl)-2,6-dichloronicotinateYield 72.2%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 5.3 g (24.1 mmol) 2,6-dichloro-4-methyl-pyridine-3-carboxylic acid methylester in CCl4 (92 ml) were added 3.1 g (26.5 mmol) N-Bromosuccinimide, 395 mg (2.4 mmol) AIBN and 1.45 ml (25.3 mmol) acetic acid. The mixture was irradiated with a 200 W Wolfram lamp at 60° C. for 24 h. Subsequently the mixture was filtered through celite and the filtrate was concentrated in vacuo. Purification of the residue by CC (hexane/EtOAc 97:3) provided 5.2 g of a mixture of 2,6-dichloro-4-methyl-pyridine-3-carboxylic acid methylester and 4-(bromomethyl)-2,6-dichloro-pyridine-3-carboxylic acid methylester which was used in subsequent reactions without further purification.

Workup

  1. filtrationSubsequently the mixture was filtered through celite
  2. concentrationthe filtrate was concentrated in vacuo
  3. customPurification of the residue by CC (hexane/EtOAc 97:3)

Sources & evidence

ORD record
ord-c56349b03be741dc97890034a3f8c417
Source dataset
uspto-grants-2016_03
Patent number
US09278103B2

Reaction notes

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