N-bromobutanimide → Methyl 2-(bromomethyl)-5-chloro-4-nitrobenzoate

HRID 2401467Notes

Reaction equation

HRID 2401467 reaction equation
[Cl:1][C:2]1[C:3]([N+:13]([O-:15])=[O:14])=[CH:4][C:5]([CH3:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].C1C(=O)N([Br:23])C(=O)C1>CC#N.CC(N=NC(C#N)(C)C)(C#N)C>[Br:23][CH2:12][C:5]1[CH:4]=[C:3]([N+:13]([O-:15])=[O:14])[C:2]([Cl:1])=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 11085581HCID 11085581, compound

Product 1

HCID 71744076Methyl 2-(bromomethyl)-5-chloro-4-nitrobenzoateYield 89%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of methyl 5-chloro-2-methyl-4-nitrobenzoate (862 mg, 4 mmol) and NBS (854 mg, 4.8 mmol) in MeCN (16 mL) was degassed and then AIBN (14 mg, 0.08 mmol) was added. The mixture was heated to 70° C. for 18 h. The solvent was removed in vacuo and the residue was partitioned between DCM (50 mL) and water (50 mL). The organic phase was passed through a hydrophobic frit and the solvent was removed in vacuo. Purification of the residue via silica gel column chromatography (0-100% EtOAc in iso-hexane) in order to remove baseline impurities gave methyl 2-(bromomethyl)-5-chloro-4-nitrobenzoate (1.09 g, 89%) as a brown oil. 1H NMR (400 MHz, CDCl3): δ 8.14 (s, 1H), 7.98 (s, 1H), 4.91 (s, 2H), 4.00 (s, 3H).

Workup

  1. customwas degassed
  2. customThe solvent was removed in vacuo
  3. customthe residue was partitioned between DCM (50 mL) and water (50 mL)
  4. customthe solvent was removed in vacuo
  5. customPurification of the residue via silica gel column chromatography (0-100% EtOAc in iso-hexane) in order
  6. customto remove baseline impurities

Sources & evidence

ORD record
ord-7ef1cf971a7b4ce1a02a11854ee4691b
Source dataset
uspto-grants-2014_08
Patent number
US08796296B2

Reaction notes

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