Bromine → Methyl 4-bromo-5-methylfuran-2-carboxylate

HRID 2392103Notes

Reaction equation

HRID 2392103 reaction equation
[CH3:1][C:2]1[O:6][C:5]([C:7]([O:9][CH3:10])=[O:8])=[CH:4][CH:3]=1.[Cl-].[Cl-].[Cl-].[Al+3].[Br:15]Br>C(Cl)(Cl)Cl>[Br:15][C:3]1[CH:4]=[C:5]([C:7]([O:9][CH3:10])=[O:8])[O:6][C:2]=1[CH3:1]

Participants

5

Reactant 3

HCID 24408BromineHCID 137628Methyl 5-methyl-2-furancarboxylateHCID 6451240Aluminum(III) Chloride

Product 1

HCID 604544Methyl 4-bromo-5-methylfuran-2-carboxylateYield 89.6%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl 5-methyl-2-furancarboxylate (1.5 g, 10.70 mmol) and aluminum trichloride (2.14 g, 16.06 mmol) in chloroform (21 ml) at 0° C. was added bromine (0.77 ml, 14.99 mmol). The resulting solution stirred at 0° C. and warmed to RT over 12 h. This reaction was run in batches (1.5 g and 1 g) and the batches were combined, added to ice and partitioned between H2O-DCM. The aqueous phase was washed several times with DCM and the combined organic fractions were dried over Na2SO4, concentrated and purified by column chromatography (0.5-10% EtOAc in hexanes) affording the title compound (2.1 g, 54%) as a white solid; LCMS (ES) m/z=219, 221 (M, M+2)+.

Workup

  1. temperaturewarmed to RT over 12 h
  2. additionadded to ice
  3. custompartitioned between H2O-DCM
  4. washThe aqueous phase was washed several times with DCM
  5. dry with materialthe combined organic fractions were dried over Na2SO4
  6. concentrationconcentrated
  7. custompurified by column chromatography (0.5-10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-5a9ad4c3d1274cf3bdeb53f86b49d6f4
Source dataset
uspto-grants-2012_09
Patent number
US08273782B2

Reaction notes

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