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.
Key words
iodoarenes - arenes - halogenation - iodine - peroxides
References 1 These results were presented at the International Symposium on Frontiers in Molecular Science 2002, Qingdao, China, July 14-18, 2002.
2a Roedig A. In
Houben-Weyl, Methoden der organischen Chemie
4th ed., Vol. 5/4:
Mueller E.
Thieme;
Stuttgart:
1960.
p.517-678
2b Merkushev EB.
Usp. Khim.
1984,
53:
583 ; Russ. Chem. Rev. 1984 , 53 , 343
2c Merkushev EB.
Synthesis
1988,
923
2d Sasson Y. In
The Chemistry of Halides, Pseudo-Halides, and Azides, Suppl. D1
Patai S.
Rappoport Z.
Wiley-Interscience;
Chichester:
1995.
p.535-620
2e Steel PG. In
Rodd’s Chemistry of Carbon Compounds
2nd ed., Part 1, Vol. 3:
Sainsbury M.
Elsevier;
Amsterdam:
1996.
p.178-224
3a Varvoglis A.
The Organic Chemistry of Polycoordinated Iodine
VCH;
Weinheim:
1992.
3b Stang PJ.
Zhdankin VV.
Chem. Rev.
1996,
96:
1123
3c Varvoglis A.
Hypervalent Iodine in Organic Synthesis
Academic Press;
San Diego:
1997.
3d Zhdankin VV.
Stang PJ.
Chem. Rev.
2002,
102:
2523
3e Wirth T.
Topics in Current Chemistry, Springer;
Berlin:
2003.
3f Stang PJ.
J. Org. Chem.
2003,
68:
2997
4a Skulski L.
Molecules
2000,
5:
1331 ; http://www.mdpi.org/molecules/papers/51201331.pdf
4b 2 (SO4 )3 , I(OSO3 H)3 , ArISO4 , and ArI(OSO3 H)2 are discussed and referred to the literature: Kasumov TM.
Koz’min AS.
Zefirov NS.
Usp. Khim.
1997,
66:
939 ; Russ. Chem. Rev. 1997 , 66 , 843
5 Skulski L.
Molecules
2003,
8:
45 ; http://www.mdpi.org/molecules/papers/80100045.pdf
6 Krassowska-Swiebocka B.
Lulinski P.
Skulski L.
Synthesis
1995,
926
7 Lulinski P.
Skulski L.
Bull. Chem. Soc. Jpn.
1997,
70:
1665
8 Lulinski P.
Skulski L.
Bull. Chem. Soc. Jpn.
1999,
72:
115
9 Lulinski P.
Skulski L.
Bull. Chem. Soc. Jpn.
2000,
73:
951
10a Kryska A.
Skulski L.
J. Chem. Res., Synop.
1999,
591
10b Kryska A.
Skulski L.
J. Chem. Res., Miniprint
1999,
2501
11 Lu C.-S.
Hughes EW.
Giguere PA.
J. Am. Chem. Soc.
1941,
63:
1507
12 Tanatar SJ.
J. Russ. Phys. Chem. Soc.
1906,
40L:
376 ; Chem. Abstr . 1909 , 3 , 383
13a
13b Aldrich Handbook of Fine Chemicals and Laboratory Equipment
Aldrich;
Milwaukee:
2003-2004.
p.1898
13c The Merck Index
12th ed.:
Merck & Co., Inc.;
Rahway:
1996.
p.10007
14 Chen J.-A.
Lin C.-S.
Liu LK.
J. Chin. Chem. Soc. (Taipei)
1996,
43:
95 ; see also refs. 9, 10 therein, Chem. Abstr. 1996 , 124 , 288874
15 Adimurthy S.
Ramachandraiah G.
Ghosh PK.
Bedekar AV.
Tetrahedron Lett.
2003,
44:
5099
16 Sosnowski M.
Skulski L.
Molecules
2002,
7:
867 ; http://www.mdpi.org/molecules/papers/71200867.pdf
17 Varied quantities of conc. H2 SO4 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. H2 SO4 had to be added to catalyze better the oxidative iodination reaction. For more details see either Note 22 in Ref.,
[9 4
18 Dictionary of Organic Compounds
6th ed.:
Chapman & Hall;
London:
1996.
19 The urea released from UHP is readily acetylated in hot Ac2 O/AcOH/concd H2 SO4 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.
20 The 1 H 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 ;
