N-bromobutanimide → 1-Bromo-2-methoxy-4-methyl-5-nitrobenzene

HRID 2200836Notes

Reaction equation

HRID 2200836 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[C:5]([CH3:12])[CH:4]=1.[Br:13]N1C(=O)CCC1=O>CC#N>[Br:13][C:8]1[CH:7]=[C:6]([N+:9]([O-:11])=[O:10])[C:5]([CH3:12])=[CH:4][C:3]=1[O:2][CH3:1]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 793303-Methyl-4-nitroanisole

Product 1

HCID 445513181-Bromo-2-methoxy-4-methyl-5-nitrobenzene

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
140 °C

Procedure

To a solution of nitrobenzene 11 (2.2 g, 13.1 mmol) in CH3CN (8 mL) in a pressure tube was added N-bromosuccinimide (8.2 g, 45.8 mmol). The tube was sealed and the contents were heated to 140° C. overnight on an oil bath. The reaction mixture turned brownish-red overnight. After the reaction was quenched with saturated aqueous Na2S2O3 solution (150 mL), the product was extracted with Et2O (2×150 mL), dried (Na2SO4), and purified by chromatography (hexane/EtOAc 3:1) to afford brominated product 12 along with other byproducts that were not separable by chromatography (hexane/EtOAc 3:1). The product mixture (2.8 g, 87%) was used directly in the next step: Rf0.29 (hexane/EtOAc 3:1); 1H NMR (CDCl3) δ 2.66 (s, 3H), 3.98 (s, 3H), 6.76 (s, 1H), 8.31 (s, 1H); 13C NMR (CDCl3) δ 21.7, 56.8, 108.9, 114.3, 125.2, 130.4, 136.3, 141.9, 159.3; ESI-HRMS [M-Br—CH3—H]− C7H6NO3 calcd for m/z 152.0348, found 152.0349.

Workup

  1. customThe tube was sealed
  2. customAfter the reaction was quenched with saturated aqueous Na2S2O3 solution (150 mL)
  3. extractionthe product was extracted with Et2O (2×150 mL)
  4. dry with materialdried (Na2SO4)
  5. custompurified by chromatography (hexane/EtOAc 3:1)

Sources & evidence

ORD record
ord-c42368eb3b72412590c08909b49eba4e
Source dataset
uspto-grants-2016_06
Patent number
US09359389B2

Reaction notes

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