Toluene → 3-Bromo-4-chlorobenzamide

HRID 657359Notes

Reaction equation

HRID 657359 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[Cl:11])[C:5](O)=[O:6].C(Cl)(=O)C(Cl)=O.C[N:19](C=O)C.C1(C)C=CC=CC=1>C(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[Cl:11])[C:5]([NH2:19])=[O:6]

Participants

6

Reactant 4

HCID 1140TolueneHCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 27355443-Bromo-4-chlorobenzoic acid

Product 1

HCID 532166633-Bromo-4-chlorobenzamide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

3-Bromo-4-chlorobenzoic acid (2.35 g, 10 mmol) was suspended in CH2Cl2 (50 mL) and stirred under argon at room temperature. Oxalyl chloride (2.53 g, 20 mmol) was added followed by DMF (10 μL). Gas evolution began, and the mixture was stirred until gas evolution ceased. 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 (10 mL). This was stirred for 30 min. The phases were separated and the organic washed 1× with brine dried over anhydrous Na2SO4, filtered, and evaporated. The residue was crystallized from EtOAc/hexane to give the title compound as a white crystalline solid. LC-MS m/z 233.7 (M+H)+, 1.54 min (ret time); mp 146-147° C.; analytical HPLC shows 100% purity, (ret time: 11.835 min).

Workup

  1. stirringthe mixture was stirred until gas evolution
  2. customto remove excess oxalyl chloride
  3. additionadded to concentrated ammonium hydroxide (10 mL)
  4. stirringThis was stirred for 30 min
  5. customThe phases were separated
  6. washthe organic washed 1× with brine
  7. dry with materialdried over anhydrous Na2SO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was crystallized from EtOAc/hexane

Sources & evidence

ORD record
ord-4b24794518394da3a50e4a633c876fc7
Source dataset
uspto-grants-2011_12
Patent number
US08071588B2

Reaction notes

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