Dimethylhydroxylamine → 4-bromo-2-chloro-N-methoxy-N-methylbenzamide

HRID 855301Notes

Reaction equation

HRID 855301 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](O)=[O:7])=[C:4]([Cl:11])[CH:3]=1.C(N(CC)C(C)C)(C)C.CN([C:24]([O:28][N:29]1N=NC2C=CC=C[C:30]1=2)=[N+](C)C)C.[B-](F)(F)(F)F.CN(C)O>CN(C=O)C.CCOCC>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([N:29]([O:28][CH3:24])[CH3:30])=[O:7])=[C:4]([Cl:11])[CH:3]=1

Participants

7

Reactant 4

HCID 27970DimethylhydroxylamineHCID 81531DiisopropylethylamineHCID 1088294-Bromo-2-chlorobenzoic acidHCID 2733207O-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate

Product 1

HCID 598430764-bromo-2-chloro-N-methoxy-N-methylbenzamideYield 96%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-bromo-2-chlorobenzoic acid (2.00 g, 8.50 mmol) in DMF (20 ml) was added N,N-diisopropylethyl amine (3.18 ml, 18.69 mmol) followed by TBTU (3.00 g, 9.34 mmol) followed by dimethylhydroxylamine (829 mg, 8.50 mmol). The reaction mixture was stirred at rt overnight and then diluted with ether and the organic layer was washed with water, 1N HCl, sat. NaHCO3, and brine. The organic layer was then dried (MgSO4), filtered and concentrated in vacuo to give a residue which was purified by flash column chromatography to give 4-bromo-2-chloro-N-methoxy-N-methylbenzamide (2.27 g, 96%) as a colorless oil. 1H NMR (CDCl3, 300 MHz): δ 7.59 (d, J=1.5 Hz, 1H), 7.45 (dd, J=1.5, 8.0 Hz, 1H), 7.22 (d, J=8.0 Hz, 1H), 3.48 (br s, 3H), 3.38 (br s, 3H).

Workup

  1. washthe organic layer was washed with water, 1N HCl, sat. NaHCO3, and brine
  2. dry with materialThe organic layer was then dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto give a residue which
  6. customwas purified by flash column chromatography

Sources & evidence

ORD record
ord-8b351cc12c7b49daa02be3f48efb7b47
Source dataset
uspto-grants-2007_08
Patent number
US07259183B2

Reaction notes

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