Toluene → 3-Bromo-4-methylbenzamide

3-Bromo-4-methylbenzoic acid (5 g, 23.25 mmol) was suspended in CH2Cl2 (100 mL) and stirred under argon at room temperature. Oxalyl chloride (5.9 g, 46.5 mmol) was added followed by DMF (20 μL). Gas evolution began, and the mixture was stirred for 2 days during which time complete solution occurred. The solvents were pumped off and toluene was added and stripped off to remove excess oxalyl chloride. The residue was taken up in EtOAc and added to concentrated ammonium hydroxide (20 mL). This was stirred for thirty min. The phases were separated and the organic washed 1× with brine dried over anhydrous Na2SO4, filtered, and concentrated. The residue was crystallized from EtOAc/hexane and dried under vacuum to afford the title compound as a white crystalline solid. LC-MS m/z 213.8 (M+H)+, 1.41 min (ret time); mp 178-179° C.

1. stirringthe mixture was stirred for 2 days during which time complete solution
2. customto remove excess oxalyl chloride
3. additionadded to concentrated ammonium hydroxide (20 mL)
4. stirringThis was stirred for thirty min
5. customThe phases were separated
6. washthe organic washed 1× with brine
7. dry with materialdried over anhydrous Na2SO4
8. filtrationfiltered
9. concentrationconcentrated
10. customThe residue was crystallized from EtOAc/hexane
11. customdried under vacuum

ORD record

ord-c6f62680c36d4d33b34f520b1e2d901e

Source dataset

uspto-grants-2011_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08067408B2