Triethylamine → 2-Bromo-5-fluoro-N-methoxy-N-methylbenzamide

HRID 51060Notes

Reaction equation

HRID 51060 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:8]([F:11])=[CH:7][C:3]=1[C:4](O)=[O:5].Cl.[CH3:13][NH:14][O:15][CH3:16].C(N(CC)CC)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[Br:1][C:2]1[CH:10]=[CH:9][C:8]([F:11])=[CH:7][C:3]=1[C:4]([N:14]([O:15][CH3:16])[CH3:13])=[O:5]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 27781812-Bromo-5-fluorobenzoic acid

Product 1

HCID 227354792-Bromo-5-fluoro-N-methoxy-N-methylbenzamideYield 73%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Bromo-5-fluorobenzoic acid (4.60 g, 0.02 mol), N,O-Dimethylhydroxylamine hydrochloride (2.05 g, 0.02 mol), carbon tertabromide (6.9 g, 0.02 mol) was added to mixture of methylene chloride (100 mL) and triethylamine (2.9 mL, 0.02 mol). Triphenylphospine (5.53 g, 0.02 mol) was added to the solution over 1 hour and stirred for another 1 hour. The solution was concentrated to an oil. Hexanes (100 mL) and Ethyl Acetate (100 mL) were added to the oil and stirred for 1 hour then filtered. The filtrate was concentrated and the residue was purified by chromatography (Hexanes/Ethyl Acetate) on silica gel to afford 2-bromo-5-fluoro-N-methoxy-N-methylbenzamide as a foamy white solid in 73% yield. 1H NMR (CDCl3, 500 MHz) δ3.00-3.98 (m, 6 H), 6.97-7.08 (m, 2H), 7.51-7.54 (m, 1H).

Workup

  1. concentrationThe solution was concentrated to an oil
  2. additionHexanes (100 mL) and Ethyl Acetate (100 mL) were added to the oil
  3. stirringstirred for 1 hour
  4. filtrationthen filtered
  5. concentrationThe filtrate was concentrated
  6. customthe residue was purified by chromatography (Hexanes/Ethyl Acetate) on silica gel

Sources & evidence

ORD record
ord-b915ed178a1f4bd791ff961406463547
Source dataset
uspto-grants-2004_03
Patent number
US06713471B1

Reaction notes

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