Mild and selective nitration of phenols by zeofen

Article abstract of DOI:10.1080/00397910701397011

Certain phenols and naphthols were nitrated regioselectively with zeofen in dichloromethane as solvent at room temperature and in a short reaction time to give good yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701397011

This article was downloaded by: [University of California Santa Cruz]
On: 11 November 2014, At: 03:39
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office:
Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International
Journal for Rapid Communication of
Synthetic Organic Chemistry
Publication details, including instructions for authors and subscription
information:
http://www.tandfonline.com/loi/lsyc20
Mild and Selective Nitration of Phenols by
Zeofen
a
b
a
Mohammad A. Bigdeli , Majid M. Heravi & Firouzeh Nemati
a
Faculty of Chemistry , Teacher Training University , Tehran, Iran
b
Department of Chemistry , School of Science, Azzahra University , Vanak,
Tehran, Iran
Published online: 03 Jul 2007.
To cite this article: Mohammad A. Bigdeli , Majid M. Heravi & Firouzeh Nemati (2007) Mild and Selective
Nitration of Phenols by Zeofen, Synthetic Communications: An International Journal for Rapid Communication
of Synthetic Organic Chemistry, 37:13, 2225-2230, DOI: 10.1080/00397910701397011
To link to this article: http://dx.doi.org/10.1080/00397910701397011
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”)
contained in the publications on our platform. However, Taylor & Francis, our agents, and our
licensors make no representations or warranties whatsoever as to the accuracy, completeness, or
suitability for any purpose of the Content. Any opinions and views expressed in this publication
are the opinions and views of the authors, and are not the views of or endorsed by Taylor &
Francis. The accuracy of the Content should not be relied upon and should be independently
verified with primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities
whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial
or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or
distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use
can be found at http://www.tandfonline.com/page/terms-and-conditions

w
Synthetic Communications , 37: 2225–2230, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701397011
Mild and Selective Nitration of Phenols
by Zeofen
Mohammad A. Bigdeli
Faculty of Chemistry, Teacher Training University, Tehran, Iran
Majid M. Heravi
Department of Chemistry, School of Science, Azzahra University, Vanak,
Tehran, Iran
Firouzeh Nemati
Faculty of Chemistry, Teacher Training University, Tehran, Iran
Abstract: Certain phenols and naphthols were nitrated regioselectively with zeofen in
dichloromethane as solvent at room temperature and in a short reaction time to give
good yields.
Keywords: nitration, phenols, zeofen
Among all electrophilic substitutions, nitration of aromatic compounds is one of
[
1–3]
the most important industrial processes
[
and is the subject of a large body of
Nitrated phenolic compounds are very important chemicals
4,5]
literature.
that have applications as solvents, dyes, pharmaceuticals, agrochemicals,
explosives, and plastics in industry. They are also useful intermediates for the
preparation of other compounds, particularly amines, by reduction of nitro
[
6]
groups.
However, the majority of reported methods for nitration of aromatic
[7]
compounds suffer from disadvantages such as low regioselectivity,
Received in Poland October 23, 2006
Address correspondence to Majid M. Heravi, Department of Chemistry, School of
Science, Azzahra University, Vanak, Tehran, Iran. E-mail: mmh1331@yahoo.com
2
225

2
226
M. A. Bigdeli, M. M. Heravi, and F. Nemati
[
8]
[9]
[10]
overnitration,
safety problems (storage, handling, using toxic transition-metal cations such
strongly acidic media,
tedious workup,
and
þ2
þ2
[11]
as Hg , Cu , etc.).
efforts to develop alternative procedures such as using solid acids, other
These disadvantages have encouraged extensive
þ
sources of NO , organic nitrating agent, and so forth.
2
[12]
[6]
X, Y,
[6,12,13]
Zeolite-based solid acid catalysts such as ZSM-5,
12–14]
and
have been studied for nitration of various activated as well as deac-
[
beta
tivated substrates.
Besides zeolites, a variety of other solid acids such as sulfuric acid
[
15]
[16–18]
supported on silica,
clay-supported metal nitrates,
and metal-modified montmorillonite KSF,
been studied for nitration of aromatic compounds.
Furthermore, alternative nitrating agents, such as nitric acid in mixed
metal-
[
19]
[20]
exchanged clays,
have
[
7]
[21]
[7]
acids; nitronium salts in organic media;
metal nitrates of Na, Ti, Zr,
and organic nitrating agent such as acetyl
nitrates have been studied. Besides the organic solvents, ionic liquids
[
22]
[23]
[24]
Fe,
Ni,
and Ce;
[
3]
[
25]
have also been used as solvent.
Considering these reactions and environmental concerns, there is
still a need for research on new reagents for regioselective nitration of
phenols.
Herein we report our results on the regioselective nitration of phenols
using zeofen. We have introduced and investigated various performances of
[
26–28]
zeofen in different reactions.
.
Zeofen can be prepared easily by a com-
bination of Fe(NO3)3 9H O (0.8 g, 2 mmol) and a weight equivalent of
2
HZSM-5 zeolite. This reagent can be stored in a dark brown bottle and be
stable for at least 6 months.
We believed that such reagent can also act as a nitrating agent, because
ferric nitrate can act as a nitrating agent along with HZSM-5 zeolite,
instead of Brønsted (H SO , HNO ) or Lewis acids (AlCl , TiCl ). HZSM-5
2
4
3
3
4
zeolite was prepared by calcinations of NHAZSM-5 zeolite at 5008C for 8 h.
The nitration reaction readily took place by adding the phenols and
zeofen in the suitable solvent in a reaction vessel and efficiently stirring
the resultant heterogeneous mixture at room temperature. The progress of
reaction was monitored by thin-layer chromatography (TLC). Upon the
completion of reaction, zeofen was separated by simple filtration. This
method thus provides nitrated phenols directly, in a short reaction time
and with good yields (Table 1). Although the nitration reaction also
.
occurs in the absence of zeolite [only with Fe(NO3)3 9H O], no selectivity
2
has been observed in this reaction. Clearly zeolite (HZSM-5) helped to
achieve high selectivity. The results are explained on the basis of
diffusion and binding of phenols inside zeolite, which bring
[
29]
regioselectivity.
In conclusion, the mononitration of phenols with zeofen has been
achieved with high regioselectivity and with excellent yields. In general,
exclusive orthoselectivity was observed for all phenols subjected to this

Mild and Selective Nitration of Phenols by Zeofen
2227
Table 1. Nitration of phenols with zeofen
a
Entry
1
Substrate
Products
Time (min)
30
Yield (%)
75
2
3
10
10
55
80
65
4
40
5
6
7
10
10
15
75
90
90
8
20
90
a
Yields are based on isolated products.

2
228
M. A. Bigdeli, M. M. Heravi, and F. Nemati
protocol.
The high regiospecifity, short reaction time, good isolated yield, and use
of inexpensive and nontoxic materials make this methodology have wide
synthetic and commercial utility.
EXPERIMENTAL
Chemicals were purchased from the Fluka, Merck, and Aldrich chemical
companies. Melting points were determined on an Electrothermal 9100 and
are not corrected. TLC on commercial aluminum-backed plates of silica gel
60 F254 was used to monitor the progress of reactions. Yields refer to isolated
pure products. The nitration products are characterized by comparison of their
1
spectral data (IR, H NMR), TLC, and melting points with authentic samples.
Nitration of Phenols with Zeofen: Typical Procedure
4-Chloro phenol (0.12 g, 1 mmol) and zeofen (1–1.5 eq.) in 3 mL of dichlor-
omethane were magnetically stirred at room temperature. After the com-
pletion of the reaction, the reaction mixture was filtered (the progress of the
reaction was monitored by TLC). The residue was washed with CH Cl2
2
(
2 ꢀ 5 mL) and dried over anhydrous sodium sulfate. The solvent was
removed under vacuum. The crude product was purified by silica-gel dry
flash chromatography using petroleum ether–ethyl acetate (98:2) as eluent.
[30]
The yield was 0.15 g (88%), mp 89–908C (lit.
mp 918C).
ACKNOWLEDGMENTS
The authors are thankful to the Teacher Training University Research Council
for the partial financial support. We are also grateful to Dr. B. Mohajerani,
Petrochemical Research Center of Iran, for a gift of zeolite.
REFERENCES
1
. Thampson, M. J.; Zeegers, P. J. Two phase nitration of phenols, part 3: The
nitration of anisole. Tetrahedron 1991, 47, 8787–8790.

Mild and Selective Nitration of Phenols by Zeofen
2229
2
3
. Bisarya, S. C.; Joshi, S. K.; Holker, A. G. Calcium nitrate—a new nitrating agent
for nuclear nitration of substituted phenols. Synth. Commun. 1993, 23, 1125–1137.
. Augusto, J.; Rodrigues, R.; Filho, A. P. O.; Custodio, M. R. Regioselectivity of the
nitration of phenols by acetonitrate adsorbed on silica gel. Tetrahedron 1999, 55,
6733–6738.
4. Hogget, J. G.; Moodie, R. B.; Penton, J. R.; Schofield, K. Nitration and Aromatic
Reactivity; Cambridge University Press: London, 1971.
5
6
. Schofield, K. Aromatic Nitration; Cambridge University Press: London, 1980.
. (a) Essakkiduria, T.; Pitchumani, K. Zeolite-mediated regioselective nitrtion of
phenols in solid state. J. Mol. Catal. A 2002, 185, 305–309; (b) Samajdar, S.;
Backer, F. F.; Banik, B. K. Surface-mediated higly efficient regioselective
nitration of aromatic compounds by bismute nitrate. Tetrahedron Lett. 2000, 41,
8017–8020; (c) Tanseem, A. M. M.; Rajanna, K. C.; Saiparakash, P. K.
Ammonium nickel sulphate mediated nitration of aromatic compounds with
nitric acid. Synth. Commun. 2001, 31, 1123–1127.
7
8
9
. Olah, G. A.; Kuhn, S. J. Aromatic substitution XII: Steric effects in nitronium salt
nitrations of alkylbenzenes and hallobenzenes. J. Am. Chem. Soc. 1962, 84,
3684–3687.
. Peng, X.; Suzuki, H.; Lu, C. Zeolite-assisted nitration of neat toluene and chloro-
benzene with a nitrogen dioxide/molecular oxegen system: Remarkable enhance-
ment of para-selectivity. Tetrahedron Lett. 2001, 42, 4357–4359.
. Ramana, M. M. V.; Malix, S. S.; Parihar, J. A. Guanidium nitrate: A novel reagent
for aryl nitrations. Tetrahedron Lett. 2004, 45, 8681–8683.
1
1
0. Strazzolini, P.; Giumanini, A. G.; Runcio, A. Nitric acid in dichloromethane
solution: Facile preparation from potassium nitrate and sulfuric acid. Tetrahedron
Lett. 2001, 42, 1387–1389.
1. (a) Olah, G. A.; Krishnamurthy, V. V.; Narang, S. C. Aromatic substitution 50:
Mercury(II)-promoted a zeotropic nitration of aromatics over nafion-H solid
super acidic catalyst. J. Org. Chem. 1982, 47, 596–598; (b) Mellor, J. M.;
Mittoo, S.; Parkes, R.; Millar, R. W. Improved nitration using metal nitrate–
sulfuric acid system. Tetrahedron 2000, 56, 8019–8024.
1
2. Choudary, B. M.; Sateesh, M.; Kantam, M. L.; Wararao, K. K.; Raghavan, K. V.;
Sarma, J.; Prasal, K. V. R. Selective nitration of aromatic compounds by solid acid
catalysts. Chem. Commun. 2000, 1, 25–26.
13. Smith, K.; Musson, A.; Deboos, G. A. A novel method for the nitration of simple
aromatic compounds. J. Org. Chem. 1998, 63, 8448–8454.
14. Bernasconi, S.; Pringruber, G. D.; Kogelbaur, A.; Prins, R. Factors determining the
suitability of zeolite BETA as para-selection nitration catalyst. J. Catal. 2003, 219,
231–241.
1
5. Zolfigol, M. A.; Madrakian, E.; Ghaemi, E. Silica sulfuric acid/NaNO as a novel
2
heterogeneous system for the nitration of phenols under mild conditions.
Molecules 2002, 7, 734–742.
1
1
6. Laszlo, P.; Pennetreau, P. Vastly improved para preference in the nitration of halo
benzenes. J. Org. Chem. 1987, 52, 2407–2410.
7. Cornelis, A.; Laszlo, P.; Pennetreau, P. Clay supported reagents, 5: Nitration of
estrone into 2-nitrostrone by clay-supported ferric nitrate. J. Org. Chem. 1983,
48, 4771–4772.
1
1
8. Giganta, B.; Prazeres, A. O.; Marcelo-Curto, M. J.; Cornelis, A.; Laszlo, P. Mild
and selective nitration by claycop. J. Org. Chem. 1995, 60, 3445–3447.
9. Choudary, B. M.; Sarma, M. R.; Kumara, K. V. Fe montmorillonite catalyst for
selective nitration of chlorobenzene. J. Mol. Catal. A 1994, 87, 33–38.
þ2

2
230
M. A. Bigdeli, M. M. Heravi, and F. Nemati
2
2
0. Yin, W.; Shi, M. Nitration of phenolic compounds by metal-modified montmoril-
lonite KSF. Tetrahedron 2005, 61, 10861–10867.
1. Uemura, S.; Toshimitsu, A.; Okaner, M. Nitration aromatic hydrocarbons and
ipso-nitrosodemetallation of aryl metal compounds in sodium nitric–trifluoroace-
tic acid. J. Chem. Soc. Perkin. Trans. 1 1978, 1076–1079.
2
2
2
2. Combes, R. G.; Russell, L. W. Nitration of aromatic compounds by tetrato titanium
(
IV) in carbon tetrachloride solution. J. Chem. Soc., Perkin. Trans. 2 1974,
30–833.
8
3. Anuradha, V.; Srinivas, P.; Aparana, P.; Madhusudana Rao, J. p-Toluensulfonic
acid catalyzed regiospecific nitration of phenols with metal nitrates. Tetrahedron
Lett. 2006, 47, 4933–4935.
4. Dincturk, S.; Ridd, J. H. Reactions of cerium(IV) ammonium nitrate with aromatic
compounds in acetonitrile, part 1: The mechanism of side-chain substitution.
J. Chem. Soc., Perkin. Trans. 2 1982, 961–964.
2
2
2
5. Laali, K. K.; Gettwert, V. J. Electrophilic nitration of aromatics in ionic liquids
solvents. J. Org. Chem. 2001, 66, 35–40.
6. Heravi, M. M.; Ajami, D.; Aghapoor, K.; Ghassemzadeh, M. Zeofen, a user-
friendly oxidizing reagent. Chem. Commun. 1999, 833–834.
7. Heravi, M. M.; Derikvand, F.; Oskooie, H.; Hekmatshoar, R. Zeofen a user-
friendly agent for oxidation of the Hantzsch 1,4-dihydropyridines. J. Chem. Res.
2
006, 37, 168–169.
2
8. Heravi, M. M.; Ajami, D.; Ghassemzadeh, M.; Tabar-Hydar, K. Zeofen, an
efficient reagent for oxidative deprotection of trimethyl silyl ethers under
microwave irradiation in solventless system. Synth. Commun. 2001, 31,
2097–2100.
9. Esakkidurai, T.; Kumarraja, M.; Pitchumani, K. Regioselective nitration of
aromatic substrates in zeolite cages. Proc. Indian Acad. Sci. (Chem. Sci.) 2003,
115, 113–121.
0. Malcolm, J.; Zeogers, T. P. J. A theoretical study on the two-phase nitration of
phenols. Tetrahedron 1989, 45, 191–202.
2
3