Pyridine → 4-bromo-N-methoxy-N,3-dimethylbenzamide

HRID 1741041Notes

Reaction equation

HRID 1741041 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](O)=[O:7])=[CH:4][C:3]=1[CH3:11].Cl.[CH3:13][NH:14][O:15][CH3:16].N1C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+]>S(Cl)(Cl)=O.ClCCl.C(#N)C>[CH3:16][O:15][N:14]([CH3:13])[C:6](=[O:7])[C:5]1[CH:9]=[CH:10][C:2]([Br:1])=[C:3]([CH3:11])[CH:4]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 10340Sodium CarbonateHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 821314-Bromo-3-methylbenzoic acid

Product 1

HCID 218337954-bromo-N-methoxy-N,3-dimethylbenzamideYield 100%

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolventHCID 24386Thionyl ChlorideSolvent

Procedure

A stirred suspension of 4-bromo-3-methylbenzoic acid (5.0 g, 0.023 mole) in thionyl chloride (20 ml) was heated under reflux for 2 hours, then concentrated in vacuo. The residual acid chloride was dissolved in dichloromethane (100 ml) and added dropwise over 10 minutes to a stirred solution of N,O-dimethylhydroxylamine hydrochloride (2.4 g, 0.025 mole) and pyridine (5.6 ml, 0.069 mole) in dichloromethane (150 ml) and acetonitrile (20 ml) at -20° C. The reaction mixture was allowed to warm to room temperature over 3 hours then treated with 10% Na2CO3 solution and extracted with dichloromethane. The extract was dried (Na2SO4) and concentrated in vacuo to afford the title compound as a pale yellow oil (5.9 g, 100%).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 2 hours
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residual acid chloride was dissolved in dichloromethane (100 ml)
  5. extractionextracted with dichloromethane
  6. dry with materialThe extract was dried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a15f6fe919264423853ca34a0345ddcb
Source dataset
uspto-grants-1999_10
Patent number
US05972951

Reaction notes

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