N-bromobutanimide → 3-Methoxy-4-nitrobenzyl bromide

HRID 2279889Notes

Reaction equation

HRID 2279889 reaction equation
[Br:1]N1C(=O)CCC1=O.[CH3:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[C:12]([O:19][CH3:20])[CH:11]=1>ClC(Cl)C.ClCCl.N(C1(C#N)CCCCC1)=NC1(C#N)CCCCC1>[Br:1][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[C:12]([O:19][CH3:20])[CH:11]=1

Participants

6

Reactant 2

HCID 67184N-bromobutanimideHCID 974555-Methyl-2-nitroanisole

Product 1

HCID 126216043-Methoxy-4-nitrobenzyl bromideYield 58.4%

Reagents, catalysts & solvents 3

HCID 749781,1'-Azobis(cyclohexanecarbonitrile)CatalystHCID 6344DichloromethaneSolventHCID 63651,1-DichloroethaneSolvent

Procedure

N-Bromosuccinimide (58.62 g, 329.34 mmol) was added in portions over a period of 5-10 min to a well stirred solution of 4-methyl-2-methoxy-1-nitro benzene (50.0 g, 299.4 mmol) and 1,1′-Azobis(cyclohexane carbonitrile) (1.0 g, 4.1 mmol) in dichloroethane (600 mL) and the resulting mixture was heated to reflux under a UV light for a maximum 7-8 hr. After cooling to rt, the reaction mixture was diluted with dichloromethane (400 mL) and washed with aqueous Na2S2O4 solution, water and brine. The organic phase was dried over anhydrous Na2SO4, filtered and concentrated to give a crude solid (102.0 g) which was triturated with diisopropyl ether to afford 43.0 g of the desired product. The diisopropyl ether filtrate was concentrated and purified by silica-gel column chromatography (5-40% EtOAc/Hexanes) to obtain an additional 5.5 g of the desired product (48.5 g, 66%). 1H NMR (CDCl3-300 MHz): δ=3.98 (s, 3H), 4.46 (s, 2H), 7.05 (dd, J=6.60 Hz, 1H), 7.10 (d, J=1.5 Hz, 1H), 7.82 (d, J=8.4 Hz, 1H).

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux under a UV light for a maximum 7-8 hr
  3. washwashed with aqueous Na2S2O4 solution, water and brine
  4. dry with materialThe organic phase was dried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a crude solid (102.0 g) which
  8. customwas triturated with diisopropyl ether

Sources & evidence

ORD record
ord-0cc642bf63e14a4cb669d3b909d151d1
Source dataset
uspto-grants-2015_09
Patent number
US09133224B2

Reaction notes

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