Benzyl chloroformate → Methyl [4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]acetate

HRID 2403071

Reaction equation

HRID 2403071 reaction equation
[CH:1]1[C:2]([CH2:19][C:20]([OH:22])=[O:21])=[CH:3][C:4]([I:18])=[C:5]([O:8][C:9]2[CH:10]=[C:11]([I:17])[C:12]([OH:16])=[C:13]([I:15])[CH:14]=2)[C:6]=1[I:7].[CH2:23](OC(Cl)=O)C1C=CC=CC=1>CO>[CH3:23][O:21][C:20](=[O:22])[CH2:19][C:2]1[CH:1]=[C:6]([I:7])[C:5]([O:8][C:9]2[CH:10]=[C:11]([I:17])[C:12]([OH:16])=[C:13]([I:15])[CH:14]=2)=[C:4]([I:18])[CH:3]=1

Participants

4

Reactant 2

HCID 10387Benzyl chloroformateHCID 65552Tetraiodothyroacetic acid

Product 1

HCID 52919069Methyl [4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]acetateYield 100%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

In anhydrous conditions, Tetrac (5.0 g, 6.7 mmol, 1.0 eq.) was dissolved in anhydrous methanol (200 mL). To the solution was then added dropwise SOCl2 (485 μL, 6.7 mmol, 1.0 eq.). The reaction was set to reflux for 2 days. Water was then added to the reaction medium (200 mL) and then the solution was concentrated to yield a precipitate. The precipitate was then collected by vacuum filtration and then recrystallized to give orange crystals (3.10 g, 4.0 mmol) of methyl-2-(4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl)acetate in 61% yield. Method B: In anhydrous conditions, Tetrac (1.0 g, 1.3 mmol, 1.0 eq.) was suspended in MeOH (20 mL). TEA (181.4 μL, 1.3 mmol, 1.0 eq.) was then added dropwise followed by benzylchloroformate (184.8 μL, 1.3 mmol, 1.0 eq.). After stirring for 30 minutes, the solution was filtered, the solvent was removed from the residue and the product was separated by silica gel chromatography (eluent=DCM). The collected fractions were then evaporated to give a white powder which was recrystallized to give orange crystals (990 mg, 1.3 mmol) of methyl-2-(4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl)acetate in a quantitative yield.

Workup

  1. filtrationthe solution was filtered
  2. customthe solvent was removed from the residue
  3. customthe product was separated by silica gel chromatography (eluent=DCM)
  4. customThe collected fractions were then evaporated
  5. customto give a white powder which
  6. customwas recrystallized

Sources & evidence

ORD record
ord-44cbec455fcd4efbacd896dc73377567
Source dataset
uspto-grants-2014_08
Patent number
US08802240B2

Linked notes

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