Methanamine, N-methoxy-, hydrochloride (1:1) → 4-bromo-N-methoxy-N,3-dimethylbenzamide

HRID 1669327Notes

Reaction equation

CO[C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([Br:10])=[C:6]([CH3:11])[CH:5]=1.Cl.[CH3:14][NH:15][O:16][CH3:17].C([Mg]Cl)(C)C>O1CCCC1>[Br:10][C:7]1[CH:8]=[CH:9][C:4]([C:3]([N:15]([O:16][CH3:17])[CH3:14])=[O:12])=[CH:5][C:6]=1[CH3:11]

Participants

Conditions

Temperature: -30 °C

Procedure

4-Bromo-3-methyl-benzoic acid methyl ester (6 g, 26.19 mmol) was dissolved into anhydrous tetrahydrofuran (THF) (200 mL) and then cooled to −30° C. while stirring under nitrogen. N,O-dimethylhydroxylamine hydrochloride (3.81 g, 39.29 mmol) was then added to the solution in one portion. Isopropyl magnesium chloride (39 mL, 2M soln. in THF, 78.6 mmol) was slowly added to the cooled suspension over 1 h. After complete consumption of starting material, then 30% solution of ammonium chloride was added with stirring. The reaction was diluted with diethyl ether and extracted. The organic layer was collected and washed with cold water (2×) and brine. The solution was then dried over anhydrous sodium sulfate, filtered, and concentrated. The 4-Bromo-N-methoxy-3,N-dimethyl-benzamide (5.94 g, 23.05 mmol) was obtained in purified form after flash column chromatography.

Workup

customAfter complete consumption of starting material
addition30% solution of ammonium chloride was added
stirringwith stirring
additionThe reaction was diluted with diethyl ether
extractionextracted
customThe organic layer was collected
washwashed with cold water (2×) and brine
dry with materialThe solution was then dried over anhydrous sodium sulfate
filtrationfiltered
concentrationconcentrated

Sources & evidence

ORD record: ord-1587a19867b34f249f5ac6d58249bd41
Source dataset: uspto-grants-2011_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07989457B2

Reaction notes

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