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

HRID 1845436Notes

Reaction equation

HRID 1845436 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[Cl:5][C:6]1[S:10][C:9]([C:11]([O:13][CH3:14])=[O:12])=[CH:8][CH:7]=1.[Br:15]Br>C(Cl)(Cl)Cl>[Br:15][C:7]1[CH:8]=[C:9]([C:11]([O:13][CH3:14])=[O:12])[S:10][C:6]=1[Cl:5]

Participants

5

Reactant 3

HCID 24408BromineHCID 589473Methyl 5-chlorothiophene-2-carboxylateHCID 6451240Aluminum(III) Chloride

Product 1

HCID 57826388Methyl 4-bromo-5-chlorothiophene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
25 °C

Procedure

To a 1 L round bottom flask was added aluminum chloride (11.32 g, 85 mmol) and methyl 5-chloro-2-thiophenecarboxylate (10 g, 56.6 mmol) dissolved in CHCl3 (250 mL). Br2 (4.08 ml, 79 mmol) was added dropwise over 10 minutes. After stirring for 6 h at 25° C., the light orange reaction solution was washed with sat NaHCO3. The organic layer was dried Na2SO4, filtered and concentrated. The residue was purified on silica gel [hexanes/EtOAc, 9:1] to give the product [12 g, 80%] as a white solid. LCMS (ES) m/z 256 (M+H)+.

Workup

  1. washthe light orange reaction solution was washed with sat NaHCO3
  2. filtrationfiltered
  3. concentrationconcentrated
  4. customThe residue was purified on silica gel [hexanes/EtOAc, 9:1]
  5. customto give the product [12 g, 80%] as a white solid

Sources & evidence

ORD record
ord-f9db8ff7f0274756a85e5a209de4e23c
Source dataset
uspto-grants-2015_02
Patent number
US08946278B2

Reaction notes

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