Chloromethyl Methyl Ether → 2-Bromo-1-methoxymethoxy-4-nitrobenzene

HRID 1357439Notes

Reaction equation

HRID 1357439 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[OH:13].Cl[CH2:15][O:16][CH3:17]>O1CCCC1>[Br:3][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[O:13][CH2:15][O:16][CH3:17]

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 221092-Bromo-4-nitrophenolHCID 24758Sodium hydride

Product 1

HCID 110973452-Bromo-1-methoxymethoxy-4-nitrobenzeneYield 310.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

4.2 g (140 mmol) of a sodium hydride dispersion (55% in oil) are added portion-wise at 0° C. to a solution of 15.3 g 2-bromo-4-nitrophenol (70 mmol) in 250 ml tetrahydrofuran. Subsequently the reaction mixture is stirred for 50 minutes at 0° C. and then mixed with 1.83 g of chloromethyl-methyl ether (19.4 mmol). The mixture is stirred for an additional hour at 0° C. and then poured into ice, extracted with ethyl acetate and the organic phase is washed with a saturated aqueous salt solution, dried over Na2SO4, filtered and concentrated. The residue so obtained is concentrated over silica gel with petroleum ether/ethyl acetate (9:1). 15.8 g (80% theoretical yield) of 2-bromo-1-methoxymethoxy-4-nitrobenzene are obtained.

Workup

  1. stirringThe mixture is stirred for an additional hour at 0° C.
  2. additionpoured into ice
  3. extractionextracted with ethyl acetate
  4. washthe organic phase is washed with a saturated aqueous salt solution
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue so obtained
  9. concentrationis concentrated over silica gel with petroleum ether/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-84885fca11654e1dbc4e650e0f4d3855
Source dataset
uspto-grants-2003_07
Patent number
US06592631B2

Reaction notes

Loading…