Under an argon atmosphere, trimethyl 2,4,6-triaminobenzene-1,3,5-tricarboxylate (1.00 g, 3.36 mmol, 1.00 equiv) was dissolved in dry acetonitrile (25 mL) and cooled to 0 °C. Tert-butyl nitrite (3.12 g, 3.60 mL, 30.3 mmol, 9.00 equiv) was added dropwise in alternation with iodo(trimethyl)silane (6.06 g, 4.12 mL, 30.3 mmol, 9.00 equiv). After complete addition, the mixture was slowly warmed to 21 °C and stirred for 16 h. Na2S2O3 solution (30 mL) and DCM (30 mL) were added to the reaction mixture and the layers were separated. The aqueous layer was extracted with DCM (2x30 mL) and the combined organic layers were washed with water (30 mL) and brine (30 mL), followed by drying over Na2SO4. After filtration, the solvent was removed under reduced pressure and the residue was purified by column chromatography (cyclohexane/ethyl acetate 5:1 to 3:1) to give trimethyl-2,4,6-triiodobenzene-1,3,5-tricarboxylate (134 mg, 213 μmol, 6% yield) as a colorless solid.
