Synthesis 2008(2): 185-187  
DOI: 10.1055/s-2007-990950
SHORTPAPER
© Georg Thieme Verlag Stuttgart · New York

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

Victor D. Filimonov*a, Nadya I. Semenischevaa, Elena A. Krasnokutskayaa, Alexei N. Tretyakova, Ho Yun Hwangb, Ki-Whan Chi*b
a Department of Organic Chemistry, Tomsk Polytechnic University, 634050 Tomsk, Russia
Fax: +7(3822)563637; e-Mail: filimonov@tpu.ru;
b Department of Chemistry, University of Ulsan, 680-749 Ulsan, Republic of Korea
e-Mail: kwchi@ulsan.ac.kr;
Further Information

Publication History

Received 14 September 2007
Publication Date:
07 December 2007 (online)

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.

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.

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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