PAPER 1467

Ecofriendly Iodination of Activated Aromatics and Coumarins Using

Potassium Iodide and Ammonium Peroxodisulfate
IodinationofActivatedAromaticsandCoumarins C. Ganguly,* Sujoy Kumar Barik, Sanjoy Dutta
Nemai
Department of Chemistry, University of Kalyani, Kalyani 741235, WB, India
Fax +91(33)25828282; E-mail: [email protected]
Received 19 January 2010; revised 1 February 2010

have been used as a hydrogen iodide trap. However, these

Abstract: An environmentally benign protocol for the iodination of
activated aromatics, such as phenols, anilines, and hydroxycou-
oxidizers are often harsh and involve toxic heavy metals,
marins, using inexpensive commercially available potassium iodide hence they are environmentally unacceptable. It was our
and ammonium peroxodisulfate (1:2.5 molar equivalents per mole aim to develop a mild, selective method for the iodofunc-
of substrate) in aqueous methanol (MeOH–H2O, 6:1) at room tem- tionalization of activated aromatics, particularly for phe-
perature has been developed. The protocol provides for ortho-selec- nols and hydroxycoumarins using commercially available
tive monoiodination as the predominant product without added acid inexpensive reagents under environmentally benign con-
and it is compatible with a number of common oxidizible functional
ditions. The oxyiodination strategy that utilizes an iodide
groups, such as formyl, benzylic C–H, aromatic amines and hy-
droxymethyl. Good to acceptable yields of monoiodinated products salt in combination with a metal-free ecofriendly oxidiz-
in acceptable reaction times and exclusive ortho-iodination for 7- ing agent appealed to us. In fact, halogenation in Nature
hydroxycoumarins, despite the presence of vinylogous electron- occurs by way of oxidative halogenation involving halo-
rich C3, are some of the key advantageous features of the method. peroxidase enzymes that oxidize halide salts into reactive

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Key words: iodination, potassium iodide, ammonium peroxodisul- hypohalous derivatives. To this end, potassium iodide in
fate, activated aromatics, coumarins combination with ammonium peroxodisulfate was an at-
tractive candidate. Potassium iodide is available in high
purity and it is less expensive than sodium and ammonium
Iodinated aromatic and heteroaromatic compounds have iodide. It can be oxidized with ammonium peroxodisul-
attracted active contemporary interest because of their fate, which is also an inexpensive, easily available re-
versatile synthetic utility ranging from precursors of orga- agent. It is a ‘green’ oxidizer that is widely used in
nometallic compounds and benzynes to substrates for pal- industry for bleaching waste water treatment and it has
ladium-, nickel-, and copper-catalyzed cross-coupling been utilized to accomplish the oxidation of alkenes,6 ben-
reactions to form C–C, C–N, C–O, and C–S bonds.1 Ad- zyl alcohols,7 and substituted aromatics,8 the cleavage of
ditionally, iodinated arenes possess a wide array of bio- procarbonyl imine derivatives, such as oximes and phe-
logical activity and find application in human and animal nylhydrazones,9 the deprotection of allyl ethers,10 and the
medicine.2 Iodophenols, for example, are extensively solid-state microwave-assisted cleavage of 1,3-dithianes
used in non-evasive medical diagnostic techniques and ra- and dithiolanes on wet montmorillonite K-10 clay.11
dioiodinated photoprobes, hence they are of immense val- Herein, we describe the results of the iodination of a wide
ue as therapeutic and diagnostic aids. Iodocoumarins are variety of aromatics and hydroxycoumarins with potassi-
utilized as fluorophores and intermediates for the synthe- um iodide and ammonium peroxodisulfate in aqueous
sis of coumarin C-ribosides that are effective photophysi- methanol (Scheme 1).
cal probes for the study of oligonucleotide dynamics.3
Recently, iodinated umbelliferones have been elaborated KI, (NH4)2S2O8 (1:2.5 molar ratio)
ArH ArI
into dihydrofuroangelicins and dihydrofuropsoralins with MeOH–H2O, r.t. or reflux
pronounced cytotoxicity against KB cells and they have
Scheme 1
properties that combat skin diseases such as psoriasis and
vitiligo.4 However, the iodofunctionalization of arenes
and heteroarenes is frequently not facile due to the weak We selected phenol as representative of activated aromat-
electrophilic nature of the iodonium ion coupled with the ics and set out to optimize the iodination conditions. Se-
relatively weak bond strength of C–I compared to C–Br lective monoiodination of phenol is elusive unless some
and C–Cl. The reversibility of the reaction with release of directive influence of substituents is operative and, there-
hydrogen iodide necessitates the use of oxidizers to make fore, it was surmised that phenol represents a substrate
it practicable. Numerous oxidizing agents, including that would give a good feel for the mildness as well as the
HgO,5a Oxone,5b Ag2SO4,5c NaIO4,5d HIO4,5e CrO3,5f selectivity of the iodinating reagent. Iodination of phenol
Pb(OAc)4,5g I2O5,5h silica–Bi(NO)3·5 H2O,5i and TlOAc,5j with KI–(NH)4S2O8 proved was unsuccessful in dry meth-
anol and also in acetonitrile (Table 1, entries 1 and 2). On
SYNTHESIS 2010, No. 9, pp 1467–1472xx. 201 the other hand, iodination with the same reagent system in
Advanced online publication: 12.03.2010 water, with and without anionic surfactant, sodium dode-
DOI: 10.1055/s-0029-1218698; Art ID: Z01010SS cyl sulfate (SDS) [H2O (5 mL), SDS (0.4 mmol)] well
© Georg Thieme Verlag Stuttgart · New York
1468 N. C. Ganguly et al. PAPER

above its critical miceller concentration (cmc), was also of methanol as solvent in iodination may be due to its sol-
disappointingly sluggish even at elevated temperatures ubilizing influence on iodine and the substrate as well.
(50–60 °C) (entries 8–10). Attempted iodination in aque- However, the possibility of liberated iodine being oxi-
ous acetonitrile (MeCN–H2O, 4:1) was also not encourag- dized to a stronger iodonium ion equivalent in the form of
ing either in terms of reaction time and yield of 2- methyl hypoiodite in the presence of an excess of a potent
iodophenol (1a) (entry 3). Aqueous methanol (6:1) was oxidizer such as peroxodisulfuric acid cannot be ruled out
found to be the medium of choice furnishing 1a and 2,6- and there is literature precedent for an analogous reaction
diiodophenol (1b) in 65% and 10% yields, respectively in in the case of benzyltrimethylammonium dichloroperio-
an acceptable reaction time (20 h) (entry 6). Observed re- date based aromatic iodinations.15
gioselectively was in sharp contrast to exclusive para-io-
dination of phenol with iodine and tetrabutylammonium Table 1 Optimization Experiments for the Oxyiodination of Phenol
persulfate12 in aprotic solvent, acetonitrile (20 °C, 30 h). Entry Ratioa KI/ Solvent Additive Time Yieldb
Whereas iodine–thallium(I) acetate5j allowed ortho-selec- (NH4)S2O8 (h) (%)
tive iodination of phenols, the present method constitutes
1a 1b
a metal-free ortho-selective iodinating system for phe-
nols. For selective monoiodination, a stoichiometric ratio 1 1:2 MeOH – 10 0 0
of substrate/iodide/oxidizer 1:1:2.5 was found to be re-
warding from an iodine atom economy standpoint. Here- 2 1:2 MeCN – 10 8 0
in, we report the results of the iodination of a wide array 3 1:2 MeOH–H2O (4:1) – 20 55 10
of activated aromatics and coumarins using this reagent
combination (Table 2). In view of the importance of poly- 4 1:1.5 MeOH–H2O (2:1) – 30 45 6
iodinated phenols in medical diagnostics, we explored tri- 5 1:2 MeOH–H2O (6:1) – 20 60 8

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iodination of phenol with 3.3 molar equivalents of
potassium iodide along with 7 molar equivalents of am- 6 1:2.5 MeOH–H2O (6:1) – 20 65 10
monium peroxodisulfate at room temperature for ten 7 1: 2 MeCN–H2O (4:1) – 20 35 8
hours and to our satisfaction, 2,4,6-triiodophenol (1c) was
isolated as the exclusive product in 88% yield (entry 1). 8 1:2 H 2O – 48 30 5
Notably, no mineral acid was added for the iodination of 9 1:2 H 2O – 40 20 8
phenols. Previously, a combination of molecular iodine
and potassium peroxodisulfate (0.5:2.2 molar ratio)13 was 10 1:2 H 2O SDS (10 cmc) 40 30 10
utilized for the synthesis of iodoarenes, but this is effec-
11 1:2 t-BuOH–H2O (6:1) – 12 32 5
tive only in the presence of concentrated sulfuric acid (3
mmol) or trifluoroacetic acid in dichloromethane as an ac- 12 1:2 AcOH–H2O (1:3) – 10 40 15c
tivator; formation of resinous products and over-oxidation a
Ratio = mol equiv ratio of KI/(NH4)S2O8 per mmol of substrate; the
for electron-rich oxidation-prone aromatics are some of iodination of phenol was carried on a 1-mmol scale.
the serious limitations of this protocol. Successful iodina- b
2-Iodophenol (1a) and 2,6-diiodophenol (1b) were products of iodi-
tion of anisole with potassium iodide and 30% hydrogen nation of phenol.
peroxide in methanol14 also required one equivalent of c
Several other products were formed in addition.
concentrated sulfuric acid to arrest the decomposition of
hydrogen peroxide to oxygen. We envisaged that the key (NH4)2S2O8 + H2O (NH4)2SO5 + H2SO4
to the efficacy of the present combination was the in situ (NH4)2S2O8 + H2SO4 H2S2O8 + (NH4)2SO4
generation of sulfuric acid upon hydrolysis of the acidic H2S2O8 + H2O H2SO5 + H2SO4
salt ammonium peroxodisulfate. Subsequent release of 2 KI + H2SO5 + H2SO4 I2 + 2 KHSO4 + H2O
peroxomonosulfuric acid (Caro’s acid) by way of hydrol- 2 KI + H2S2O8 2 KHSO4 + I2
ysis of peroxodisulfuric acid and oxidation of iodide to io- Scheme 2
dine by either of the peracids under the acidic conditions
follow. Oxidation of iodide to iodine with peroxodisulfu-
ric acid and Caro’s acid are not mutually exclusive and ortho-Iodination of phenol is tentatively due to the hydro-
may compete with each other (Scheme 2). To support our gen-bonding interaction of the phenolic OH with MeOI
contention, a solution of ammonium peroxodisulfate (2 through a six-membered transition state thereby promot-
mmol) in methanol–water (6:1, 4 mL) was found to exhib- ing delivery of iodine at C2 (Scheme 3). However, this is
it a pH of 1.19 at 33 °C; addition of potassium iodide (1 a purely hypothetical suggestion at this stage of the inves-
mmol) to it sharply increased its pH to 6.43. These obser- tigation. In case of 3-methylphenol the mono/diiodinated
vations coupled with the fact that this combination proved product ratio (3a/3b) was almost identical to that for 1a/
ineffective in dry methanol strongly suggest the crucial 1b, ortho-monoiodinated product, 2-iodo-5-methylphe-
role of water in the iodination process. The actual iodinat- nol, predominating in 60% yield (Table 2, entry 3).
ing species involved is not clear to us. The facilitating role

Synthesis 2010, No. 9, 1467–1472 © Thieme Stuttgart · New York

PAPER Iodination of Activated Aromatics and Coumarins 1469

Table 2 Oxidative Iodination of Activated Aromatics and Coumarins with Potassium Iodide and Ammonium Peroxodisulfate

Entry Substrate Timea (h) Product(s) [yieldb (%)]

OH OH
OH
I I
1 (i) 20

1a (65) 1b (10) I

OH
I I

(ii) 10c 1b (40) 1c (8) I

(iii) 10d
1c (88)

OH OH
OH
I I I

2 16

2a (70) 2b (8)
OH
OH

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OH I
I
3 12

I
3a (60) 3b (10)

OH
OH OH
I
4 12
OH
OH OH
I
4a (65) 4b (15)

I
OH OH
5 12

5a (95)
OH
OH
6 15

I
6a (92)

OH
OH OH
I I
I
7 20

CHO
CHO CHO
7a (80) 7b (5)

OH
OH
I OMe
OMe
8 12

CHO
CHO
8a (80)

Synthesis 2010, No. 9, 1467–1472 © Thieme Stuttgart · New York

1470 N. C. Ganguly et al. PAPER

Table 2 Oxidative Iodination of Activated Aromatics and Coumarins with Potassium Iodide and Ammonium Peroxodisulfate (continued)

Entry Substrate Timea (h) Product(s) [yieldb (%)]

OH
OH
I
9 6

CH2OH
CH2OH
9a (92)
OMe
OMe
10 16

I
10a (92)

OMe
OMe

11 10
OMe
OMe I
11a (90)

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12 12

I
12a (94)

NH2 NH2
NH2 I
13 16e

I I
13a (55) 13b (8)

NH2 NH2
NH2
I I I

14 10

14a (68) 14b (10)

NMe2
NMe2
15 10

I
15a (58)
I
HO O O HO O O
16 20

16a (85)

I
HO O O HO O O
17 24

17a (87)

Synthesis 2010, No. 9, 1467–1472 © Thieme Stuttgart · New York

PAPER Iodination of Activated Aromatics and Coumarins 1471

Table 2 Oxidative Iodination of Activated Aromatics and Coumarins with Potassium Iodide and Ammonium Peroxodisulfate (continued)

Entry Substrate Timea (h) Product(s) [yieldb (%)]

O O
O O
18 18c
H2N
H2N I
18a (75)
I

19 12c O
HO O O O O

19a (66)
I

20 HO O O 12c O O O

20a (68)

a
Reaction conditions: substrate/KI/(NH4)2S2O8 1:1:2.5, MeOH–H2O (6:1), r.t.

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b
Yields refer to the chromatographically pure products characterized by spectral data (FT-IR, 1H and 13C NMR, and EIMS).
c
Reaction conditions: substrate/KI/(NH4)2S2O8 1:1:2:5, MeOH–H2O (6:1), 50–60 °C.
d
Reaction conditions: substrate/KI/(NH4)2S2O8 1:3.3:7, MeOH–H2O, r.t.
e
Reaction conditions: substrate/KI/(NH)2S2O8 1:1:1.5, MeOH–H2O, r.t.

ortho-Selectivity was further demonstrated in the iodina- 4-methyl group. Notably, exclusive bromination at C3 of
tion of benzene-1,3-diol which furnished 2-iodobenzene- 7-hydroxycourmarin was accomplished by us with N-bro-
1,3-diol (4b) in 15% yield despite unfavorable steric situ- mosuccinimide in molten tetrabutylammonium bro-
ation (entry 4). Oxidation-prone aromatic aldehydes and mide,17 a hydrogen-bond base that discourages hydrogen
benzylic alcohol remained intact during the iodination bond formation of N-bromosuccinimide with the 7-OH
(entries 7–9). However, in case of aniline, the use of 2.5 group thereby preventing ortho-selective bromination.
equivalents of oxidizer led to substantial formation of in- For substrates 8-allyl-7-hydroxycoumarin and 8-allyl-7-
tractable colored oxidized products and successful para hydroxy-4-methylcoumarin bearing an allyl moiety ortho
iodination was achieved only by its careful dropwise ad- to the 7-OH group, iodolactonization took precedence
dition to a stoichiometric combination of potassium io- over slower ring iodination process furnishing angular
dide and ammonium peroxodisulfate in 1:1.5 molar ratio furanocoumarins (entries 19 and 20).
(entry 13). Iodination of N,N-dimethylaniline led to 4- In conclusion, a mild ecofriendly protocol for the monoio-
iodo-N,N-dimethylaniline (15a) as the only isolable prod- dination of activated aromatics and coumarins using po-
uct (entry 15). However, formation of the violet coloration tassium iodide and ammonium peroxodisulfate has been
characteristic of Methyl Violet dye was observed upon ad- developed. Use of commercially available, inexpensive
dition of N,N-dimethylaniline to the reagent system. Pre- reagents, simple procedure, good to acceptable yields and
vious attempted of iodination of N,N-dimethylaniline with ortho-selective iodination for phenols and hydroxycou-
iodine–thallium(I) acetate5j resulted in the formation of marins without use of metal salts are key attractive fea-
15a, but the reaction was complicated due to the oxidation tures of the protocol.
of N,N-dimethylaniline to 4,4¢-methylenebis(N,N-dimeth-
ylaniline) and Methyl Violet. Analogous oxidation of
H
N,N-dimethylaniline with iodine–silver(I) trifluoroace- O O O
Me
tate–dichloromethane16 gave N,N,N¢,N¢-tetramethylbenzi- I H
I
dine. + MeOH

Iodination of 7-hydroxycoumarins (entries 16 and 17) was

sluggish as expected due to the deactivating effect of the
a-pyrone moiety, but it is remarkable that ortho-monoio-
OH
dination occurred exclusively in the benzenoid ring de-
I
spite substantial electron withdrawal to the vinylogous C3
position from the 7-OH group and this is so particularly
for 7-hydroxy-4-methylcoumarin where C3 becomes fur-
Scheme 3
ther electron-rich due to the presence of electron-releasing
Synthesis 2010, No. 9, 1467–1472 © Thieme Stuttgart · New York
1472 N. C. Ganguly et al. PAPER

KI and (NH4)2S2O8 were procured from Merck, Germany and SRL, References
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way of a research fellowship. Facilities provided by DST-FIST and
UGC-SAP Grant, Government of India are also acknowledged.

Synthesis 2010, No. 9, 1467–1472 © Thieme Stuttgart · New York