Triethylamine → HCID 22117812, compound

HRID 1668736Notes

Reaction equation

HRID 1668736 reaction equation
C(N1C=CN=C1)(N1C=CN=C1)=O.[Br:13][C:14]1[CH:15]=[C:16]([CH:20]=[CH:21][C:22]=1[Cl:23])[C:17](O)=[O:18].C(N(CC)CC)C.Cl.[CH3:32][NH:33][O:34][CH3:35]>ClCCl.O>[Br:13][C:14]1[CH:15]=[C:16]([CH:20]=[CH:21][C:22]=1[Cl:23])[C:17]([N:33]([O:34][CH3:35])[CH3:32])=[O:18]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 682631,1'-CarbonyldiimidazoleHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 27355443-Bromo-4-chlorobenzoic acid

Product 1

HCID 22117812HCID 22117812, compoundYield 79.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Carbonyldiimidazole (7.2 g, 0.045 mol) was added in portions to a stirred suspension of 3-bromo-4-chlorobenzoic acid (10.0 g, 0.042 mol) in dichloromethane (120 mL). The reaction mixture was stirred at room temperature for 30 minutes then at reflux for 30 minutes. Triethylamine (6.3 mL, 0.045 mol) and N,O-dimethylhydroxylamine hydrochloride (4.2 g, 0.043 mol) were added and the reaction mixture was stirred at room temperature overnight, then diluted with water (75 mL) and the layers separated. The aqueous fraction was extracted with dichloromethane (2×50 mL) and the combined organic extracts were washed with citric acid (10%; 2×50 mL), NaHCO3 (50 mL) and brine (50 mL), dried (sodium sulfate) and concentrated to give 3-bromo-4-chloro-N-methoxy-N-methylbenzamide as a colourless oil (9.3 g, 79%). 1H NMR (300 MHz; DMSO-d6) 7.98 (1H, s, Ar), 7.60 (1H, d, J 7.2, Ar), 7.48 (1H, d, J 7.2, Ar), 3.54 (3H, s, Me), 3.36 (3H, s, Me).

Workup

  1. temperatureat reflux for 30 minutes
  2. stirringthe reaction mixture was stirred at room temperature overnight
  3. customthe layers separated
  4. extractionThe aqueous fraction was extracted with dichloromethane (2×50 mL)
  5. washthe combined organic extracts were washed with citric acid (10%; 2×50 mL), NaHCO3 (50 mL) and brine (50 mL)
  6. dry with materialdried (sodium sulfate)
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-f10b7de0545b4c6183997f7f1968c00b
Source dataset
uspto-grants-2011_08
Patent number
US07989449B2

Reaction notes

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