Nonmetal-catalyzed iodination of arenes with iodide and hydrogen peroxide

Article abstract of DOI:10.1055/s-2004-829136

Oxidative iodination of arenes was carried out with one equivalent of KI and two equivalents of 30% hydrogen peroxide in MeOH in the presence of strong acid. Reactions of various substituted anisoles, phenols and anilines, as well as mesitylene and uracil, were selective and effective with very good yields of isolated halogenated aromatic molecules.

Full text of DOI:10.1055/s-2004-829136

PAPER
1869
Nonmetal-Catalyzed Iodination of Arenes with Iodide and Hydrogen Peroxide
N
onmetal-
e
Catalyze
d
r
Iodinatio
n
n
of
A
renes
e
w
ith Iodide
j
and Hydroge
I
n
Perox
s
ide kra,* Stojan Stavber, Marko Zupan
Laboratory for Organic and Bioorganic Chemistry, Jozef Stefan Institute and Faculty of Chemistry and Chemical Technology, University
of Ljubljana, Jamova 39, 1000 Ljubljana, Slovenia
Fax +386(1)4773811; E-mail: jernej.iskra@ijs.si
Received 29 March 2004
Abstract: Oxidative iodination of arenes was carried out with one
equivalent of KI and two equivalents of 30% hydrogen peroxide in
MeOH in the presence of strong acid. Reactions of various substi-
Equation 1
tuted anisoles, phenols and anilines, as well as mesitylene and
uracil, were selective and effective with very good yields of isolated
halogenated aromatic molecules.
Key words: iodination, haloperoxidation, hydrogen peroxide, oxi-
dative halogenation, aromatics
Equation 2
Equation 3
Halogenated organic molecules are important compounds
in pharmaceutical and agricultural chemistry,1 and they
are important synthetic intermediates in chemical synthe-
sis, especially for C-C coupling reactions.2 The use of mo-
lecular halogens for direct halogenation has drawbacks in
the difficult and dangerous handling of chlorine and bro-
mine, while iodine is less reactive. Nature has solved this
problem by evolving haloperoxidases, enzymes that oxi-
dize halide salts into reactive hypohalous derivatives.3 Its
counterpart in chemistry, named oxidative halogenation,
has been utilized for iodination with a plethora of catalysts
and oxidants in combination with molecular iodine or less
frequently with a metal iodide.1,4
lize only 30% H2O2 for iodination of arenes with KI with-
out addition of any metal catalyst.
We chose anisole as a model arene and the first experi-
ment was the simplest one; we used only anisole, 30%
H2O2 and KI in MeOH (10 mL). Immediately after addi-
tion of oxidant, bubbles started to evolve abundantly, in-
dicating the decomposition of H2O2 instead of oxidation
of iodide. Therefore we added H2SO4 acid in order to neu-
tralize the hydroxide formed during oxidation of iodide
and at the same time to activate H2O2. This proved to be
an excellent choice since addition of one equivalent of
concentrated H2SO4 completely inhibited the decomposi-
tion of H2O2 and promoted the iodination process, result-
ing in the regioselective formation of 4-iodoanisole after
17 hours at 60 °C. The important role of the acidity in io-
dination with H2O2–KI is clearly shown on Figure 1,
where it could be seen that quantitative conversion was
achieved by the addition of no less than 1.5 molar equiv-
alents of H2SO4 and 4-iodoanisole was isolated in 93%
yield. A weaker acid like HOAc did not inhibit decompo-
sition of H2O2 and reaction proceeded in an identical man-
ner as in the absence of acid.
Hydrogen peroxide has enormous potential as a green ox-
idant from which the only waste product is water.5 There
is some hazard connected with the use of concentrated so-
lutions and this risk could be avoided by applying 30%
aqueous H2O2. However, for oxidative halogenation of
arenes this requires the use of a metal catalyst for activa-
tion.4b,6 In the nonmetal-catalyzed haloperoxidation with
H2O2 and hydrohalic acid the only waste product is water
(Equation 1) which presents a clear case of green chemi-
cal reaction. Until now, this reaction with aromatic mole-
cules was reported only with HBr and HCl with an excess
of oxidant or acid.7 The use of HI is limited by its instabil-
ity while utilization of its salt has no such difficulties. In
this case of haloperoxidation, hydroxide is formed during
reaction (Equation 2). If acid is added to the reaction sys-
tem, it could serve for activation of H2O2, generation of HI
in situ and at the same time neutralization of hydroxide
formed (Equation 3).
Due to the pronounced effect of fluorinated alcohols on
the activity of H2O2,8 we tried to apply hexafluoroisopro-
panol and trifluoroethanol as solvents for the above men-
tioned reaction. Unfortunately, the solubility of molecular
iodine formed during the process is very low in these sol-
vents and it precipitated during reaction. Iodination was
consequently very slow. Reaction in MeCN was found to
be also slower and conversion was incomplete after 24
hours of reflux. On the other hand, water could be a suit-
able solvent and quantitative iodination of anisole was
also achieved in the mixture of H2O–MeOH (4:1).
As the nonmetal-catalyzed oxidative iodination of aro-
matic molecules with H2O2 has not been reported yet, it
seemed to be the most promising task. Our aim was to uti-
SYNTHESIS 2004, No. 11, pp 1869–1873
x
x.
x
x
.
2
0
0
4
Advanced online publication: 01.07.2004
DOI: 10.1055/s-2004-829136; Art ID: Z06904SS
© Georg Thieme Verlag Stuttgart · New York

1870
J. Iskra et al.
PAPER
Next, we have examined the reaction scope of H2O2–KI–
H2SO4 system for various aromatic molecules. As could
be seen from Table 1 (entries 1–4), representative meth-
oxy substituted aromatic derivatives were quantitatively
and regioselectively transformed to the corresponding io-
dides without formation of diiodinated products, while io-
dination of deactivated anisoles like 4-bromoanisole
failed under the mentioned reaction conditions.
Target aromatic molecules bearing hydroxy substituents
could also be iodinated by this method. Here, 4-tert-but-
ylphenol was converted regioselectively to the 2-iodo de-
rivative, but further iodination to 2,6-diiodo-4-tert-
butylphenol was also observed (Table 1, entry 5). Com-
Figure 1 The effect of the amount of acid on the iodination of ani- plete formation of 2,6-diiodo-4-tert-butylphenol was
sole with 1 equiv KI, 2 equiv 30% H2O2 and H2SO4 in MeOH.
achieved by using four equivalents of 30% H2O2, two
equivalents of KI and 1.5 equivalents of H2SO4 (entry 6).
2-Naphthol was also selectively converted to the corre-
Table 1 Oxidative Iodination of Arenes with the 30% H2O2–KI–H2SO4–MeOH Systema
Entry
1
Substrate
MX
KId
KId
KId
KId
KI
Condition
r.t., 3 h
Product
Conversion (%)b Yield (%)c
Anisole
4-Iodo-anisole
100
100
100
100
80
93
2
1,3-Dimethoxybenzene
1-Methoxynaphthalene
2-Methoxynaphthalene
4-tert-Butylphenol
r.t., 3 h
4-Iodo-1,3-dimethoxybenzene
4-Iodo-1-methoxynaphthalene
1-Iodo-2-methoxynaphthalene
4-tert-Butyl-2-iodo-phenol
4-tert-Butyl-2,6-diiodophenol
1-Iodo-2-hydroxynaphthalene
2-Iodo-4-nitrophenol
97
3
60 °C, 3 h
60 °C, 3 h
40 °C, 2 h
40 °C, 2 h
0 °C, 1 h
60 °C, 2 h
60 °C, 2 h
r.t., 6 h
94
4
90
5
60, 19
88
6
2 KIe
KI
100
100
60
7
2-Hydroxynaphthalene
4-Nitrophenol
93
8
KI
42, 18
90
9
2 KIe
KI
2,6-Diiodo-4-nitrophenol
4-tert-Butyl-2-iodo-aniline
4-Iodoaniline
100
85
10
11
12
13
14
15
16
17
18
19
4-tert-Butylaniline
70, 7
96
Aniline
KI
r.t., 4 h
100
100
100
100
100
100
100
100
100
KIf
KI
r.t., 4 h
94
4-Nitroaniline
60 °C, 5 h
60 °C, 3 h
0 °C, 5 h
r.t., 1 h
2-Iodo-4-nitroaniline
98
4-Trifluoromethylaniline
m-Phenylenediamine
KI
2-Iodo-4-trifluoromethylaniline
2,4-Diamino-1-iodobenzene
2,4-Diamino-1,5-diiodobenzene
2,4-Diamino-1,3,5-triiodobenzene
2-Iodo-1,3,5-trimethylbenzene
Iodouracil
90
KI
80
2KIe
3KIg
KI
91
50 °C, 1 h
60 °C, 24 h
40 °C, 24 h
95
1,3,5-Trimethylbenzene
Uracil
88
KI
90
a Substrate–KI–H2O2–H2SO4 = 1:1:2:1.
b Determined by 1H NMR spectrospcopy of crude product.
c Yield of isolated products after flash chromatography; second number the yield of diiodinated product isolated by column chromatography.
d Substrate–MX–H2O2–H2SO4 = 1:1:2:1.5.
e Substrate–MX–H2O2–H2SO4 = 1:2:4:1.5.
f Solvent system used was H2O–MeOH (4:1).
g Substrate–MX–H2O2–H2SO4 = 1:3:6:2.
Synthesis 2004, No. 11, 1869–1873 © Thieme Stuttgart · New York

PAPER
Nonmetal-Catalyzed Iodination of Arenes with Iodide and Hydrogen Peroxide
1871
1H NMR (300 MHz, CDCl3): d = 3.92 (s, 3 H), 6.51 (d, J = 8.2 Hz,
1 H), 7.47 (ddd, J = 8.2, 6.9, 1.3 Hz, 1 H), 7.55 (ddd, J = 8.3, 6.8,
1.4 Hz, 1 H), 7.90 (ddd, J = 8.3, 1.3, 0.7 Hz, 1 H), 7.98 (ddd, J = 8.2,
1.4, 0.7 Hz, 1 H), 8.20 (d, J = 8.2 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 55.6, 88.1, 105.5, 122.4, 125.9,
126.5, 128.1, 131.7, 134.6, 136.8, 156.2.
sponding 1-iodo derivatives, while 4-nitrophenol showed
the same reactivity pattern as its tert-butyl analogues (en-
tries 8, 9).
Very attractive results of application of this eco-friendly,
inexpensive and easy to use method of iodination were
also obtained when aromatic amines were tested as the
target molecules. An amino group present on the aromatic
ring was found to be compatible with this method and
anilines were iodinated in quantitative yields without the
need to protect the amino functionality (entries 10–17).
Interestingly, m-phenylenediamine was converted selec-
tively to the mono-, di- and tri-iodinated products in very
good yields (entries 15–17). With aniline, reaction was
conducted in water with 20% of MeOH to increase the
solubility of iodine formed during the reaction. Work-up
in this case requires only addition of a 0.5 M solution of
sodium thiosulfate and filtration of the precipitated aniline
derivatives, representing an additional attribute of this
clean chemical transformation (entry 12). Mesitylene and
uracil were also selectively and effectively iodinated us-
ing KI as the iodine atom source (entries 18 and 19).
MS: m/z (%) = 284 (100), 269 (42), 241 (43), 157 (21), 114 (77), 14
(22).
HRMS: m/z calcd for C11H9IO: 263.9698; found: 263.9705.
1-Iodo-2-methoxynaphthalene
White crystals; mp 82–84 °C (Lit.12 mp 88 °C).
1H NMR (300 MHz, CDCl3): d = 3.98 (s, 3 H), 7.16 (d, J = 8.9 Hz,
1 H), 7.36 (ddd, J = 8.2, 6.9, 0.8 Hz, 1 H), 7.52 (ddd, J = 8.5, 6.9,
0.7 Hz, 1 H), 7.71 (dd, J = 8.2, 0.7 Hz, 1 H), 7.78 (d, J = 8.9 Hz, 1
H), 8.13 (dd, J = 8.5, 0.8 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 57.2, 87.7, 112.9, 124.3, 128.1,
128.2, 129.8, 130.3, 131.1, 135.6, 156.6.
MS: m/z (%) = 284 (100), 241 (32), 142 (40), 114 (36).
HRMS: m/z calcd for C11H9IO: 283.9698; found: 283.9690.
4-tert-Butyl-2-iodophenol
Red oil.13
Chemicals and solvents were obtained from commercial sources
1H NMR (300 MHz, CDCl3): d = 1.27 (s, 9 H), 6.91 (d, J = 8.6 Hz,
1 H), 7.25 (dd, J = 8.6, 2.3 Hz, 1 H), 7.63 (d, J = 2.3 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 31.4, 34.0, 85.5, 114.5, 127.3,
135.0, 145.5, 152.5.
and were used as received. Silica gel 60 (60–200 mm mesh) was
1
used for column chromatography. H and 13C NMR spectra were
measured on a Varian Unity-300 spectrometer with TMS and
CDCl3 as internal standards, respectively. Melting points were de-
termined on a Büchi 535 apparatus and are uncorrected. Mass spec-
tra were acquired on an AutoSpec hybrid spectrometer.
MS: m/z (%) = 276 (28), 261 (100), 233 (10), 134 (30).
HRMS: m/z calcd for C10H13IO: 276.0011; found: 276.0022.
Oxidative Iodination of Arenes; General Procedure
4-tert-Butyl-2,6-diiodophenol
Red oil.14
Concd H2SO4 acid (3 mmol) was dissolved in MeOH (10 mL); sub-
strate (2 mmol) and KI (2 mmol) were added into the solution. Fi-
nally, 30% H2O2 (4 mmol) was added and stirred. After the reaction
was finished, the reaction mixture was poured into CH2Cl2 (30 mL),
organic phase was washed with 0.1 M NaHSO3 (20 mL), water (20
mL), dried (Na2SO4) and solvent was evaporated. Crude reaction
1H NMR (300 MHz, CDCl3): d = 1.25 (s, 9 H), 7.64 (s, 2 H).
13C NMR (300 MHz, CDCl3): d = 31.2, 33.9, 82.1, 136.3, 147.3,
151.2.
MS: m/z (%) = 402 (36), 387 (100), 260 (20).
1
product was analysed by H NMR spectroscopy and purified by
HRMS: m/z calcd for C10H12I2O: 401.8978; found: 401.8991.
flash chromatography or by column chromatography if diiodo prod-
uct was formed. Structure of products was determined by 1H and 13
NMR, MS and confirmed by HRMS.
C
1-Iodo-2-naphthol
Grey crystals; mp 87–88 °C (Lit.11 mp 92–93.5 °C).
1H NMR (300 MHz, CDCl3): d = 7.22 (d, J = 8.7 Hz, 1 H), 7.35
(ddd, J = 8.1, 6.9, 1.1 Hz, 1 H), 7.51 (ddd, J = 8.5, 6.9, 1.3 Hz, 1 H),
7.69 (d, J = 8.7 Hz. 1 H), 7.70 (dd, J = 8.1, 1.3 Hz, 1 H), 7.90 (dd,
J = 8.5, 1.1 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 86.2, 116.4, 124.1, 128.1, 128.3,
129.6, 130.2, 130.6, 134.7, 153.7.
4-Iodoanisole
Yellow crystals; mp 46–48 °C (Lit.9 mp 51–53 °C).
1H NMR (300 MHz, CDCl3): d = 3.76 (s, 3 H), 6.67 (d, J = 9.0 Hz,
2 H), 7.55 (d, J = 9.0 Hz, 2 H).
MS: m/z (%) = 234 (100), 219 (31), 191 (12), 92 (18).
4-Iodo-1,3-dimethoxybenzene
MS: m/z (%) = 270 (100), 144 (28), 127 (10), 115 (73).
HRMS: m/z calcd for C10H7IO: 269.9542; found: 269.9550.
White crystals; mp 36.5–37.5 °C (Lit.10 mp 40–41 °C).
1H NMR (300 MHz, CDCl3): d = 3.79 (s, 3 H), 3.84 (s, 3 H), 6.31
(dd. J = 8.6, 2.7 Hz, 1 H), 6.42 (d, J = 2.7 Hz, 1 H), 7.61 (d, J = 8.6
Hz, 1 H).
2,6-Diiodo-4-nitrophenol
Orange crystals; mp 150–151 °C (Lit.15 mp 155.5 °C).
13C NMR (300 MHz, CDCl3): d = 55.5, 56.2, 74.1, 99.2, 106.9,
1H NMR (300 MHz, CDCl3): d = 8.60 (s).
13C NMR (300 MHz, CDCl3): d = 80.8, 134.8, 140.7, 159.0.
139.1, 158.8, 161.3.
MS: m/z (%) = 264 (100), 221 (11), 122 (22), 107 (26).
HRMS: m/z calcd for C8H9IO2: 263.9647; found: 63.9655.
MS: m/z (%) = 391 (100), 361 (23), 218 (38), 127 (20), 91 (27), 62
(33).
HRMS: m/z calcd for C6H3I2NO: 390.8202; found: 390.8209.
4-Iodo-1-methoxynaphthalene
Yellow crystals; mp 52–53 °C (Lit.11 mp 55–55.5 °C).
Synthesis 2004, No. 11, 1869–1873 © Thieme Stuttgart · New York

1872
J. Iskra et al.
PAPER
HRMS: m/z calcd for C6H7IN2: 233.9654; found: 233.9661.
4-tert-Butyl-2-iodoaniline
Red oil.16
2,4-Diamino-1,5-diiodobenzene19
Grey crystals; mp 88 °C (decomp).
1H NMR (300 MHz, DMSO): d = 6.23 (s, 1 H), 7.53 (s, 1 H).
13C NMR (300 MHz, DMSO): d = 69.0, 99.2, 145.2, 149.0.
MS: m/z (%) = 360 (100), 254 (17), 233 (17), 106 (19).
HRMS: m/z calcd for C6H6I2N2: 359.8621; found: 359.8611.
1H NMR (300 MHz, CDCl3): d = 1.25 (s, 9 H), 6.68 (d, J = 8.3 Hz,
1 H), 7.16 (dd, J = 8.3, 2.2 Hz, 1 H), 7.61 (d, J = 2.2 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 31.4, 33.8, 84.5, 114.4, 126.5,
135.6, 143.2, 144.2.
MS: m/z (%) = 275 (37), 260 (100), 133 (29).
HRMS: m/z calcd for C10H14IN: 275.0171; found: 275.0177.
Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C,
20.2; H, 1.67; N, 7.61.
4-tert-Butyl-2,6-diiodoaniline
Red oil.16
1H NMR (300 MHz, CDCl3): d = 1.23 (s, 9 H), 7.61 (s, 2 H).
13C NMR (300 MHz, CDCl3): d = 31.3, 33.7, 81.7, 136.5, 143.7,
144.6.
2,4-Diamino-1,3,5-triiodobenzene
Grey crystals; mp 127 °C (decomp).
1H NMR (300 MHz, DMSO): d = 7.72 (s, 1 H).
MS: m/z (%) = 401 (62), 386 (100), 259 (20), 132 (25), 117 (16).
HRMS: m/z calcd for C10H13I2N: 400.9138; found: 400.9147.
13C NMR (300 MHz, DMSO): d = 66.7, 69.6, 145.2, 147.5.
MS: m/z (%) = 486 (100), 359 (18), 261 (16).
HRMS: m/z calcd for C6H5I3N2: 485.7587; found: 485.7599.
4-Iodoaniline
Brown crystals; mp 55–56.5 °C (Lit.11 mp 62.5–63 °C).
Anal. Calcd m/z for C6H5I3N2: C, 14.83; H, 1,04, N, 5.77; found: C,
15.02; H, 0.98; N, 5.56.
1H NMR (300 MHz, CDCl3): d = 6.45 (d, J = 8.8 Hz, 2 H), 7.39 (d,
J = 8.8 Hz, 2 H).
13C NMR (300 MHz, CDCl3): d = 79.3, 117.2, 137.8, 146.0.
MS: m/z (%) = 219 (25), 127 (10), 92 (64), 65 (100).
HRMS: m/z calcd for C6H6IN: 218.9545; found: 218.9551.
2-Iodo-1,3,5-trimethylbenzene
White crystals; mp 29.5–30.5 °C (Lit.20 31 °C).
1H NMR (300 MHz, CDCl3): d = 2.22 (s, 3 H), 2.42 (s, 6 H), 6.87
(s, 2 H).
13C NMR (300 MHz, CDCl3): d = 20.6, 29.5, 105.9, 127.9, 137.3,
141.7.
2-Iodo-4-trifluoromethylaniline
Orange crystals; (Lit.17 mp 50–50.5 °C).
MS: m/z (%) = 246 (33), 160 (84), 128 (64), 64 (100).
HRMS: m/z calcd for C9H11I: 245.9906; found: 245.9912.
1H NMR (300 MHz, CDCl3): d = 6.72 (dd, J = 8.4, 0.7 Hz, 1 H),
7.36 (ddd, J = 8.4, 1.4, 0.7 Hz, 1 H), 7.86 (d, J = 1.4 Hz, 1 H).
13C NMR (300 MHz, CDCl3): d = 82.1, 113.5, 121.4 (q, J = 33 Hz),
123.5 (q, J = 271 Hz), 126.5 (q, J = 3 Hz), 136.2 (q, J = 4 Hz), 149.5.
5-Iodouracil
White crystals; mp 225 °C (decomp) (Lit.21 198 °C).
MS: m/z (%) = 287 (100), 160 (37), 140 (15), 113 (10).
1H NMR (300 MHz, DMSO): d = 7.87 (s).
HRMS: m/z calcd for C7H5F3IN: 286.9419; found: 286.9427.
13C NMR (300 MHz, DMSO): d = 66.8, 150.0, 153.1, 161.9.
MS: m/z (%) = 238 (100), 195 (52), 168 (28), 152 (15), 127 (11).
HRMS: m/z calcd for C4H3N2O2I: 237.9239; found: 239.9232.
Anal. Calcd for C7H5F3IN: C, 29.29; H, 1.79; N, 4.88. Found: C,
29.48; H, 1.79; N, 4.76.
2-Iodo-4-nitroaniline
Yellow crystals; mp 98–100 °C (Lit.18 107 °C).
1H NMR (300 MHz, DMSO): d = 6.71 (d, J = 9.0 Hz, 1 H), 8.05 (dd,
J = 9.0, 2.4 Hz, 1 H), 8.55 (d, J = 2.4 Hz, 1 H).
13C NMR (300 MHz, DMSO): d = 60.4, 112.2, 124.0, 125.7, 135.4,
153.4.
Acknowledgment
The financial support from the Ministry of Science and Technology
of the Republic of Slovenia is acknowledged. We are grateful to Dr.
Dusan Zigon and Dr. Bogdan Kralj for HRMS measurements and to
Mrs. T. Stipanovic and Prof. Dr. B. Stanovnik for elemental analy-
sis.
MS: m/z (%) = 264 (72), 234 (44), 218 (18), 127 (15), 107 (16), 91
(100), 63 (55).
HRMS: m/z calcd for C6H5IN2O2: 263.9396; found: 263.9493.
References
2,4-Diamino-1-iodobenzene19
Grey crystals; mp 81 °C (decomp).
1H NMR (300 MHz, DMSO): d = 5.70 (dd, J = 8.3, 2.5 Hz, 1 H),
6.04 (d, J = 2.5 Hz, 1 H), 7.10 (d, J = 8.3 Hz, 1 H).
13C NMR (300 MHz, DMSO): d = 67.1, 99.9, 106.8, 138.1, 148.3,
149.6.
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Synthesis 2004, No. 11, 1869–1873 © Thieme Stuttgart · New York

PAPER
Nonmetal-Catalyzed Iodination of Arenes with Iodide and Hydrogen Peroxide
1873
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