Diisopropylamine → 3-Bromo-N-methoxy-N-methylbenzamide

HRID 2240995Notes

Reaction equation

HRID 2240995 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5](Cl)=[O:6].Cl.[CH3:12][NH:13][O:14][CH3:15].C(NC(C)C)(C)C>C(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([N:13]([O:14][CH3:15])[CH3:12])=[O:6]

Participants

5

Reactant 3

HCID 7912DiisopropylamineHCID 74377Benzoyl chloride, 3-bromo-HCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)

Product 1

HCID 121628753-Bromo-N-methoxy-N-methylbenzamideYield 89.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 3-bromobenzoyl chloride (20 g, 91.1 mmol) in CH2Cl2 was added dropwise to a cold (0° C.) solution of N,O-dimethylhydroxylamine hydrochloride (33.6 g, 319 mmol), diisopropylamine (98 mL, 551 mmol) in CH2Cl2 over 1 hour. The stirring continued at room temperature for 30 minutes then concentrated under vacuo. The resultant residue was dispersed in water and extracted with ethyl ether. The organic extracts were combined, dried over MgSO4 and concentrated in vacuo. This residue was purified on silica gel (ISCO) using hexanes/EtOAc (4/1) as the eluting solvent to give 3-bromo-N-methoxy-N-methylbenzamide as light yellow solid (20 g, 89% yield). m/e (M+H)+ 244. 1H NMR (400 MHz, DMSO-d6) δ ppm, 3.21 (s, 3H), 3.50 (s, 3H), 7.37-7.39, (m, 1H), 7.53-7.55 (m, 1H), 7.64-7.66 (m, 1H), 7.67-7.69 (m, 1H).

Workup

  1. concentrationthen concentrated under vacuo
  2. additionThe resultant residue was dispersed in water
  3. extractionextracted with ethyl ether
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThis residue was purified on silica gel (ISCO)

Sources & evidence

ORD record
ord-1e6462eedf094b1e8bd8c7a03b0f5935
Source dataset
uspto-grants-2010_05
Patent number
US07723368B2

Reaction notes

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