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

HRID 1753893Notes

Reaction equation

HRID 1753893 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-32fe9ccd75934ad19559f33948dcb330
Source dataset
uspto-grants-2015_10
Patent number
US09168259B2

Reaction notes

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