Eco-friendly Oxidative Iodination of Various Arenes with a Urea-Hydrogen Peroxide Adduct (UHP) as the Oxidant [1]

Abstract

Three easy eco-friendly laboratory procedures are presented for the oxidative iodination of various activated and deactivated arenes with molecular iodine, in the presence of UHP (percarbamide), a stable, strongly H-bonded, solid urea-hydrogen peroxide adduct as the oxidant.

iodoarenes - arenes - halogenation - iodine - peroxides

References

<A NAME="RT10603SS-1">1</A>

These results were presented at the International Symposium on Frontiers in Molecular Science 2002, Qingdao, China, July 14-18, 2002.

Reviews on aromatic iodination:

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<A NAME="RT10603SS-2D">2d</A> Sasson Y. In The Chemistry of Halides, Pseudo-Halides, and Azides, Suppl. D1   Patai S. Rappoport Z. Wiley-Interscience; Chichester: 1995.  p.535-620  

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<A NAME="RT10603SS-17">17</A>

Varied quantities of conc. H₂SO₄ added to the reaction mixtures (established by us experimentally and given in the experimental section for each of the arenes iodinated) clearly depended on relative reactivities of the arenes investigated. The more deactivated the arene, the more conc. H₂SO₄ had to be added to catalyze better the oxidative iodination reaction. For more details see either Note 22 in Ref., [9] or (better) Ref., [4] pp 1334-1337.

<A NAME="RT10603SS-18">18</A> Dictionary of Organic Compounds   6th ed.:  Chapman & Hall; London: 1996. 

<A NAME="RT10603SS-19">19</A>

The urea released from UHP is readily acetylated in hot Ac₂O/AcOH/concd H₂SO₄ mixtures to give N-acetylurea ad-mixed with N,N′-diacetylurea. However, these side products are fully removable from the crude iodinated products during the workup and recrystallization.

<A NAME="RT10603SS-20">20</A>

The ¹H NMR solution spectra run in this work to support the structures of the purified iodinated products are presented and discussed in: Lulinski P.; Ph.D. Thesis (in Polish); Faculty of Pharmacy, Medical University of Warsaw: Poland, 2002;