Sulfonic Acid Based Cation-Exchange Resin: A Novel Proton Source for One-Pot Diazotization-Iodination of Aromatic Amines in Water

Abstract

A convenient and simple one-pot method for the preparation of iodoarenes at room temperature has been developed, by sequential diazotization-iodination of aromatic amines with NaNO₂/KI in the presence of a sulfonic acid based cation-exchange resin in water. This inexpensive, noncorrosive and eco-friendly synthetic route is general in nature and allows for the preparation of iodo­arenes with an electron-donating or -withdrawing group in various positions from the corresponding amines in 50-98% yields.

Key words

iodoarenes - aromatic amines - diazotization - potassium iodide - sodium nitrite - cation-exchange resin

References

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6

KU-2-8 (Russia) and Trilite SPC-160H (South Korea) were used as cation-exchange resins. No significant difference was found in the result of reactions with these two resins.

7

Previous reaction conditions and yields: 1a: tert-BuSNO₂/KI/C₆H₆, 80%;¹⁰ NaNO₂/HBF₄/KI/DMSO, 90%;¹¹ NaNO₂/HBF₄/Me₃SiI/MeI, 91%;¹² i-C₅H₁₁NO₂/CH₂I₂, 90%;¹³
NO₂ (liq)/NaI/MeCN/-20 °C, 98%;¹⁴ i-C₅H₁₁NO₂/o-benzene-disulfonimide/Bu₄NI/MeCN, 92%;¹⁵ NaNO₂/KI/MeCN, 82%.^5b 2a: KNO₂/HI/DMSO, 89%;^5a NaNO₂/KI/MeCN, 81%.^5b 7a: NO₂ (liq)/anhyd KI, 100% (potentially explosive!).¹⁶ 8a: NaNO₂/HCl/KI, 67%;¹⁷ NaNO₂/KI/MeCN, 50%.^5b 9a: NaNO₂/KI/MeCN, 80%.^5b