Nitration of some aromatic compounds by sodium nitrate in the presence of benzyltriphenylphosphonium peroxodisulfate

Article abstract of DOI:10.1080/00397910701481179

A simple, mild, and regioselective method for the nitration of some aromatic compounds using sodium nitrate in the presence of benzyltriphenylphosphonium peroxodisulfate in acetonitrile as solvent is reported. Mild reaction conditions and good to excellent yields of the products are the noteworthy advantages of the method. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701481179

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Nitration of Some Aromatic Compounds
by Sodium Nitrate in the Presence of
Benzyltriphenylphosphonium Peroxodisulfate
Hassan Tajik a b , Mohammad Ali Zolfigol c , Jalal Albadi a b & Ramin Eslami a
b
a Department of Chemistry , Guilan University , Guilan, Iran
b Persian Gulf University , Bushehr, Iran
c College of Chemistry, Bu Ali Sina University , Hamadan, Iran
Published online: 14 Aug 2007.
To cite this article: Hassan Tajik , Mohammad Ali Zolfigol , Jalal Albadi & Ramin Eslami (2007) Nitration
of Some Aromatic Compounds by Sodium Nitrate in the Presence of Benzyltriphenylphosphonium
Peroxodisulfate, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 37:16, 2771-2776, DOI: 10.1080/00397910701481179
To link to this article: http://dx.doi.org/10.1080/00397910701481179
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Synthetic Communicationsw, 37: 2771–2776, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701481179
Nitration of Some Aromatic Compounds
by Sodium Nitrate in the Presence
of Benzyltriphenylphosphonium
Peroxodisulfate
Hassan Tajik
Department of Chemistry, Guilan University, Guilan, Iran and Persian
Gulf University, Bushehr, Iran
Mohammad Ali Zolfigol
College of Chemistry, Bu Ali Sina University, Hamadan, Iran
Jalal Albadi and Ramin Eslami
Department of Chemistry, Guilan University, Guilan, Iran and Persian
Gulf University, Bushehr, Iran
Abstract: A simple, mild, and regioselective method for the nitration of some aromatic
compounds using sodium nitrate in the presence of benzyltriphenylphosphonium per-
oxodisulfate in acetonitrile as solvent is reported. Mild reaction conditions and good to
excellent yields of the products are the noteworthy advantages of the method.
Keywords: aromatic compounds, benzyltriphenylphosphonium peroxodisulfate,
nitration, phenols, sodium nitrate
The nitration of aromatic compounds has received considerable attention in
organic synthesis and industrial processes.[1] Nitration typically requires the
use of a mixture of concentrated or fuming sulfuric acid with nitric acid,
leading to an excessive waste stream. Therefore, many methods have been
Received in the U.K. August 4, 2006
Address correspondence to Hassan Tajik, Department of Chemistry, Guilan Univer-
sity, Iran and Persian Gulf University, Bushehr, Rasht, Guilan 41335-1914, Iran.
E-mail: tajik@guilan.ac.ir or hasan_tajik@yahoo.com
2771

2772
H. Tajik et al.
a
Table 1. Nitration of some aromatic compounds with NaNO3 in the presence of
benzyltriphenylphosphonium peroxodisulfate in acetonitrile
Entry
1
Substrate
Product(s)
Time (h)
1.5
Yieldb
100
2
3
4
5
2.5
5.5
2
100
100
95
2
90
6
3
90
7
8
3.5
3
80c
80
9
65
70c
10
9
100
(continued)

Nitration of Aromatic Compounds
2773
Table 1. Continued
Entry
11
Substrate
Product(s)
Time (h)
8.5
Yieldb
100
12
13
4
100
100
2.5
14
3
100
15
16
10
5
80
95
17
6
75c
aMolar ratio of substrate/BTPPPDS/NaNO3, 1:1:1.2.
bConversion.
cIoslated yield.
reported in which regioselectivity, overnitration, and competitive oxidation of
substrates have been the subject of investigation.[2–9]
In the previous research, we have used peroxodisulfate ion as an
oxidant in the iodination and bromination of aromatic compounds, which
showed excellent regioselectivity.[10,11] We performed the nitration
reaction in the presence of this oxidant and hoped to obtain good results.
Therefore, we have used sodium nitrate as the source of nitrate and benzyl-
triphenylphosphonium peroxodisulfate as an oxidant[12] for the nitration of

2774
H. Tajik et al.
some activated aromatic compounds in acetonitrile as solvent. The progress
of the reactions was monitored by thin-layer chromatography (TLC) or gas
chrometography (GC). According to the obtained results, this method can
be used as a useful addition to the present methodologies for the mild
and regioselective nitration of phenols and methoxyarenes (Table 1,
Scheme 1).
All the reactions were performed under reflux conditions. According to
the obtained results, p-methoxyphenol, o-methoxyphenol, and o-chlorophenol
were converted quantitatively to the corresponding nitro products (Table 1,
entries 1–3), Phenol, 3-methoxyphenol, 1-naphthol, 2-naphthol, 2,4-dihy-
droxybenzoic acid, and salicylic acid were also reacted, and the corresponding
products were obtained in good yields (Table 1, entries 4 and 9). Anisole,
2-methylanisole, 3-methylanisole, 1,2,4-trimethoxybenzene, and 1,2,3-tri-
methoxybenzene were quantitatively converted to their corresponding
mononitrated products (Table 1, entries 10–14). 3-Chloroanisole, 1-methoxy-
naphthaline, and 2-methoxynaphthalene gave the corresponding nitrated
products in 80, 90, and 70% yields respectively. Cleavage of ether linkage
in methoxy moiety of described substrates was not observed. Resorcinol
and cathechol gave side products. Therefore, this system is not suitable for
the mononitration of these substrates.
Scheme 1.

Nitration of Aromatic Compounds
2775
In conclusion, the easy procedure, simple workup, and excellent to good
yields of the products will make this method a useful addition to the available
methodologies.
EXPERIMENTAL
All of the products were characterized by comparison of their physical and
spectral data with those of known samples[13] or analyzed using GC or mass
spectroscopy. All chemicals were purchased from Merck or Fluka chemical
companies. Benzyltriphenylphosphonium peroxodisulfate was prepared
according to the previously reported procedure.[14]
Nitration of Aromatic Compounds with NaNO3 in the Presence
of Benzyltriphenylphosphonium Peroxodisulfate in Acetonitrile
as Solvent: General Procedure
To a mixture of aromatic compounds (1 mmol) and NaNO3 (1.2 mmol) in
acetonitrile (5 mL), benzyltriphenylphosphonium peroxodisulfate (1 mmol)
was added, and the resulting mixture was stirred at reflux conditions for 1.5
to 10 h. The progress of reaction was monitored by TLC (eluent: ether/
CCl4, 3:7) or GC (capillary column). After completion of the reaction, the
mixture was filtered, and the filtrate was separated and diluted with n-
hexane (5.0 mL). The resulting solution was transferred to a separatory
funnel and washed with aqueous solution of Na2S2O3 (0.1 M, 10 mL) and
then H2O (10 mL). The organic layer was separated and dried over
anhydrous Na2SO4 (5 g). Evaporation of the solvent under reduced pressure
gave the pure product.
ACKNOWLEDGMENT
We are thankful to Guilan University and University of Persian Gulf Research
Council for the partial support of this work.
REFERENCES
1. Schofield, K. Aromatic Nitrations; Cambridge University Press: Cambridge, 1980.
2. Dagade, S. P.; Kadam, V. S.; Dongare, M. K. Catal. Commun. 2002, 3, 67.
3. Bak, R. R.; Smallridge, A. J. Tetrahedron Lett. 2001, 42, 6767.
4. Zolfigol, M. A.; Madrakian, E.; Ghaemi, E. Synlett. 2003, 14, 2222.
5. Kamal, A.; Ashwini Kumar, B.; Arifuddin, M.; Patrick, M. Ultrason. Sonochem.
2004, 11, 445.
6. Hajipour, A. R.; Ruoho, A. E. Tetrahedron Lett. 2005, 46, 8307.

2776
H. Tajik et al.
7. Anuradha, V.; Srinivas, P. V.; Aparna, P.; Rao, J. M. Tetrahedron Lett. 2006,
47, 4933.
8. Selvam, J. J. P.; Suresh, V.; Rajesh, K.; Reddy, S. R.; Venkateswarlu, Y. Tetra-
hedron Lett. 2006, 47, 2507.
9. Yin, W. P.; Shi, M. Tetrahedron 2005, 61, 10861.
10. Tajik, H.; Mohammadpoor-Baltork, I.; Rafiee Rasht-Abadi, H. Synth. Commun.
2004, 34, 3579.
11. Tajik, H.; Mohammadpoor Baltork, I.; Hassanzadeh, P.; Rafiee Rashtabadi, H.
Russian Journal of Organic Chemistry, in press.
12. Hajipour, A. R.; Ruoho, A. E. Phosphorus, Sulfur Silicon Relat. Elem. 2003,
178, 1277.
13. Weast, R. C. Handbook of Chemistry and Physics; CRC Press: Boca Raton,
FL, 1977.
14. Hajipour, A. R.; Ruoho, A. E. Phosphorus, Sulfur Silicon Relat. Elem. 2003,
178, 1277.