Iodine → Methyl 4-iodo-5-methylthiophene-2-carboxylate

HRID 1508493Notes

Reaction equation

HRID 1508493 reaction equation
[CH3:1][C:2]1[S:6][C:5]([C:7]([O:9][CH3:10])=[O:8])=[CH:4][CH:3]=1.[I:11]I>CO.S([O-])([O-])(=O)=O.[Ag+2]>[I:11][C:3]1[CH:4]=[C:5]([C:7]([O:9][CH3:10])=[O:8])[S:6][C:2]=1[CH3:1]

Participants

5

Reactant 2

HCID 807IodineHCID 580756Methyl 5-methyl-2-thiophenecarboxylate

Product 1

HCID 59014058Methyl 4-iodo-5-methylthiophene-2-carboxylate

Reagents, catalysts & solvents 2

HCID 178418844HCID 178418844, compoundCatalystHCID 887MethanolSolvent

Procedure

To a solution of methyl 5-methylthiophene-2-carboxylate (287 mg, 1.837 mmol) in MeOH (7 mL), was added silver sulfate (687 mg, 2.205 mmol) and I2 (513 mg, 2.021 mmol). The mixture was stirred at room temperature under N2 overnight. The reaction was quenched with sat. Na2SO3. The aqueous layer was extracted with EtOAc (3×). The combined organic layers were washed with brine (1×), dried (Na2SO4) and concentrated in vacuo. This was purified by flash chromatography (Biotage Horizon, 25M, Si, ˜20 mL/min, 100% hexanes for 144 mL, gradient to 10% EtOAc in hexanes over 1140 mL) to afford in order of elution methyl 4-iodo-5-methylthiophene-2-carboxylate. LCMS calc.=207.1. found=206.9 (M+Na)+. 1H NMR (500 MHz, CDCl3): δ 767 (s, 1H); 3.87 (s, 3H); 2.46 (s, 3H).

Workup

  1. customThe reaction was quenched with sat. Na2SO3
  2. extractionThe aqueous layer was extracted with EtOAc (3×)
  3. washThe combined organic layers were washed with brine (1×)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThis was purified by flash chromatography (Biotage Horizon, 25M, Si, ˜20 mL/min, 100% hexanes for 144 mL, gradient to 10% EtOAc in hexanes over 1140 mL)

Sources & evidence

ORD record
ord-e5f9487a8ed146999b97333c11e20a6e
Source dataset
uspto-grants-2015_12
Patent number
US09221834B2

Reaction notes

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