Water → HCID 71513519, compound

HRID 2401454Notes

Reaction equation

HRID 2401454 reaction equation
[CH3:1][O:2][C:3]1[C:4]([N+:14]([O-:16])=[O:15])=[CH:5][C:6]([CH3:13])=[C:7]([CH:12]=1)[C:8]([O:10][CH3:11])=[O:9].C1C(=O)N([Br:24])C(=O)C1.C(Cl)Cl.O>CC#N.CC(N=NC(C#N)(C)C)(C#N)C>[Br:24][CH2:13][C:6]1[CH:5]=[C:4]([N+:14]([O-:16])=[O:15])[C:3]([O:2][CH3:1])=[CH:12][C:7]=1[C:8]([O:10][CH3:11])=[O:9]

Participants

7

Reactant 4

HCID 962WaterHCID 6344DichloromethaneHCID 67184N-bromobutanimideHCID 71513518HCID 71513518, compound

Product 1

HCID 71513519HCID 71513519, compoundYield 31.4%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of methyl 5-methoxy-2-methyl-4-nitrobenzoate (1.11 g, 5 mmol) and NBS (1.07 g, 6 mmol) in MeCN (20 mL) was degassed and then AIBN (18 mg, 0.11 mmol) was added. The mixture was heated to 70° C. for 18 h. DCM (50 mL) and water (50 mL) were added and the organic phase was passed through a hydrophobic frit. The solvent was removed in vacuo and 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-methoxy-4-nitrobenzoate (477 mg, 31%) as an off-white solid. LCMS (10 cm_ESCI_Bicarb_MeCN): [M−Br]−=224 at 3.92 min. 1H NMR (400 MHz, CDCl3): δ 7.92 (s, 1H), 7.66 (s, 1H), 4.88 (s, 2H), 4.02 (s, 3H), 4.00 (s, 3H).

Workup

  1. customwas degassed
  2. customThe solvent was removed in vacuo and purification of the residue via silica gel column chromatography (0-100% EtOAc in iso-hexane) in order
  3. customto remove baseline impurities

Sources & evidence

ORD record
ord-488b12f200e54476ae178c1a0b2bf998
Source dataset
uspto-grants-2014_08
Patent number
US08796296B2

Reaction notes

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