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 mins. The phases were separated and the organic phase washed 1× with brine, dried over anhydrous Na2SO4, filtered, and evaporated. 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).

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 mins
5. customThe phases were separated
6. washthe organic phase washed 1× with brine
7. dry with materialdried over anhydrous Na2SO4
8. filtrationfiltered
9. customevaporated
10. customThe residue was crystallized from EtOAc/hexane
11. customdried under vacuum

ORD record

ord-e768ef4701bb4fadbb6e81e80abc8348

Source dataset

uspto-grants-2011_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08071588B2