Clay supported ammonium nitrate "clayan": A new reagent for selective nitration of arenes

Article abstract of DOI:10.1081/SCC-120021840

The nitration of activated, deactivated and highly functionalized arenes is described using clay-supported ammonium nitrate in the presence of perchloric acid.

Full text of DOI:10.1081/SCC-120021840

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Clay Supported Ammonium Nitrate “Clayan”: A
New Reagent for Selective Nitration of Arenes
H. M. Meshram , Y. S. S. Ganesh , A. V. Madhavi , B. Eshwaraiah , J. S. Yadav &
D. Gunasekar
To cite this article: H. M. Meshram , Y. S. S. Ganesh , A. V. Madhavi , B. Eshwaraiah , J. S. Yadav
& D. Gunasekar (2003) Clay Supported Ammonium Nitrate “Clayan”: A New Reagent for
Selective Nitration of Arenes, Synthetic Communications, 33:14, 2497-2503, DOI: 10.1081/
SCC-120021840
To link to this article: http://dx.doi.org/10.1081/SCC-120021840
Published online: 20 Aug 2006.
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 14, pp. 2497–2503, 2003
Clay Supported Ammonium Nitrate ‘‘Clayan’’:
A New Reagent for Selective Nitration of Arenes#
1
1
H. M. Meshram,1, Y. S. S. Ganesh, A. V. Madhavi,
*
B. Eshwaraiah,1 J. S. Yadav,1 and D. Gunasekar2
1Indian Institute of Chemical Technology,
Hyderabad, Andhra Pradesh, India
2Department of Chemistry, S. V. University,
AndhraPradesh, India
ABSTRACT
The nitration of activated, deactivated and highly functionalized
arenes is described using clay-supported ammonium nitrate in the
presence of perchloric acid.
Key Words: Aromatic nitration; Clayan; Selective; Eco-friendly.
#IICT Communication No. 4107.
*Correspondence: H. M. Meshram, Indian Institute of Chemical Technology,
Tarnaka, Hyderabad, Andhra Pradesh, India, 500 007; E-mail: hmmeshram@
yahoo.com.
2497
DOI: 10.1081/SCC-120021840
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2498
Meshram et al.
+
+
HClO
NOClO
4
NO
4
R
1
R
1
R
1
NOClO4
(O)
R
2
NO
R2
NO
2
R
2
1or 2
3
or 4
Scheme 1.
The nitration of aromatics is an important reaction in organic synth-
esis. It is generally performed either with nitrating mixture or by using
salts of heavy metals,[1] which encounter the problem of disposal waste.
In the wake of literature demand, our approach was to device a selective
nitration method using inexpensive, nonmetallic reagent with minimum
disposal waste. In continuation of our work on solid supported
reagents,[2] herein we wish to provide a new and simple alternative for
the selective nitration of arenes using ‘‘Clayan’’ in perchloric acid. An
important purpose of this work is to refocus attention on the excellent
ability of clay supported ammonium nitrate for the systematic study of
nitration of activated, deactivated and highly functionalized molecules.
Nitrates in the presence of acidic clay are known to decompose into
NOþ. So we presume that the NOþ combines with HClO4 to give nitrosyl
perchlorate, which further reacts with arenes to give nitroso arenes.
Subsequent oxidation of this leads to the nitro arene.[4]
The reaction of benzene with ‘‘Clayan’’ in the presence of perchloric
acid, gives less yield of mono nitro benzene, but the increase of alkyl
chain on benzene ring, yields are gradually increased. Further examina-
tion of highly activated systems like anisole reacts instantaneously and
gave p:o isomers (3:1, Table 1 Entry: 8) along with demethylated nitro
product (7%).[5] However, deactivated system like nitrobenzene failed to
react in the same reaction condition.
We have noticed the rapid reactivity profile of anisole and
unreactivity of nitrobenzene. Further examination of the substrate,
having both electrons donating as well as electron withdrawing groups
(Table 2 Entry: 1, 2), the reaction is indeed sluggish and proceeds at
higher temperature (50ꢀC). This may be because of the competitive
effect of both activating and deactivating the functional groups.
To support the selectivity of the present method towards the highly
functionalized substrates having functional groups like amides and alde-
hydes (Table 1: Entry 15; Table 2: Entry 3, 6) have been successfully
nitrated. This protocol may find application in the synthesis of bioactive

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Clay Supported Ammonium Nitrate
2499

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2500
Meshram et al.
Table 2. Selective mononitration of substituted arenes.
Isolated
yield
(%)a
Time Temperature
(ꢀC)
Entry no. 3d Substrate (min)
4d Product (s)
OH
NO2
OH
(a)
1
90
50
95
(a)
NO2
NO2
NO
2
2
3
90
50
60
-do-
73b
69c
OH
(b)
(c)
CHO
CHO
100
NO2
(c)
OH
OH
OMe
NO
2
4
5
75
90
27
60
86
72
OMe
(d)
(d)
OMe
OMe
CN
CN
COOH
COOH
OMe
OMe
OMe
(e)
(f)
(e)
(f)
OMe
NO2
O
O
6
7
90
45
60
75
78
NH2
NH2
OH
OH
OCH
NO2
OCH
3
3
NO
2
(g)
(g)
COOH
COOH
aYield of product after the column chromatography.
b23% of the 2,6-dinitrophenol is observed.
c8% of 2-nitro-3-hydroxy benzaldehyde is observed.
dBold numbers given in the table are compounds numbers.
molecules.[6] When benzamide is treated with clayan and perchloric acid
ꢀ
a t 70C for 2 h, after workup starting material is recovered. However,
the introduction of hydroxyl group (Table 2: Entry 6) ortho to the
amide, leads to the nitrated product even at lower temperature.

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Clay Supported Ammonium Nitrate
2501
Similarly, the nitration of benzaldehyde (Table 1: Entry 14) gives
poor yield of nitro product whereas the nitration of meta or ortho
hydroxy benzaldehyde proceeds smoothly with good yield. (Table 1:
Entry 15; Table 2: Entry 3).
The additional feature of the procedure is strengthened, by exempli-
fying the nitration of haloarenes. Though various methods[1] are known
for the nitration of halobenzenes, the thrust for the improvement in the
p-selectivity has been always a demanding task.[7] The present procedure
gives p isomer in good yield, (i.e., high p/o ratio) which is in contrast
with metallic nitrate[8a] and Menke condition.[8,9] Moreover nitration of
iodobenzene[9e] in very short time, shows the remarkable efficiency of
present procedure (Table 1: Entry 11).
To extend the scope of the present method, we have examined the
nitration of nitrile-substituted arenes. Nitration of benzonitrile gives the
relatively less yield (Table 1: Entry 12) with mononitration, (G.C 97%)
but extending the length of nitrile with carbon chain, (Table 1: Entry 13)
the yield is boosted. Further, introduction of electron rich substituents
(Table 2: Entry 4) in benzene ring enhances the yield in a highly selective
fashion (G.C 92%).
In conclusion, we have demonstrated an alternative, convenient, and
inexpensive method for the nitration of a variety of arenes using clay
supported ammonium nitrate. The method is applicable to activated
and deactivated arenes and also shows remarkable improvement in selec-
tivity. It is worth to mention that the nonmetallic nature of the reagent
and aqueous medium with minimum waste effluent shows the environ-
mental consciousness. We have provided examples of nitration for highly
functionalized arenes of biologically importance, which makes this new
procedure a very attractive alternate in pharmaceutical industry. Further
work is in progress to extend this procedure for other heterocyclic, and
polynuclear compounds.
EXPERIMENTAL
Melting points were determined on Buchi R535 apparatus and are
uncorrected. IR spectrawere recorded on either Perkin-Elmer spectro-
1
photometer or by the IR Nicole 740 FT-IR. H NMR was recorded in
Gemini 200 MHz using TMS as an internal standard. M/s recorded on
Micromass 7070h or Finnigan Mat1020 B mass spectrometer operating
at 70-eV. Thin layer chromatography was done on precoated silica gel
60f 254 (0.5 mm) glass plates.

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2502
Meshram et al.
Typical Experimental Procedure
Arene (1 mmol) was mixed with ‘‘Clayan’’[3] (192 mg, 1.2 mmol of
ammonium nitrate present in the reagent), cooled to 0ꢀC, and perchloric
acid (3 mL, 60% w/v) was added dropwise. Slurry was stirred for the
stipulated time (see table) and the reaction was monitored by tlc. After
completion of the reaction, reaction mixture was diluted with water,
neutralized with bicarbonate solution (10%), filtered and leached with
ethylacetate (2 Â 10 mL). Organic layer was separated and dried over
magnesium sulphate. Evaporation of the solvent gave the crude product,
which was column purified by ethyl acetate:hexane mixture (20:80).
Spectral Data of Selected Compounds
2,4-Dinitrophenol (4a). M.p. observed 111–113ꢀC (Literature[10a]
113ꢀC). 1H NMR (CDCl3, 200 MHz) ꢀ: 11.06 (1H, s), 9.08 (1H, d,
J ¼ 2.68), 8.48 (1H, dd, J ¼ 9.15, 2.77, 2.52), 7.36 (1H, d, J ¼ 10.7).
EI-MS m/z 184 (Mþ).
2-Nitro-3,5-dimethoxybenzylcyanide (4d). M.p. observed 112–114ꢀC
(Literature[8b] 111–113ꢀC). H NMR (200 MHz, CDCl3) ꢀ: 3.98 (3H, s),
1
4.06 (3H, s), 4.25 (2H, s), 7.12 (1H, s), 7.75 (1H, s). EI-MS m/z 222 (Mþ),
206 (M-O), 176 (M-NO2).
2,3-Dimethoxy-5-nitrobenzoicacid (4e). M.p. observed 173–174ꢀC
(Literature[8c] 174–175ꢀC). H NMR (200 MHz, CDCl3), ꢀ: 8.56 (1H, d,
1
J ¼ 2.45). 7.9 (1H, d, J ¼ 2.69), 4.18–4.20 (3H, s), 4.06–4.1 (3H, s). EI-MS
m/z 227 (Mþ).
2-Hydroxy-3-nitrobenzamide (4f ).8d 1H NMR (200 MHz, CDCl3) ꢀ:
12.25 (1H, s), 8.576 (1H, dd, J ¼ 5.94, 1.96.), 8.346 (1H, dd, J ¼ 6.59,
1.71), 7.267 (1H, t, J ¼ 8.06, 2.28, 5.78); EI-MS m/z 182 (Mþ).
4-Methoxy-3-nitro benzoic acid (4g). M.p. observed 185–187ꢀC
(Literature[8a] 186–187ꢀC). H NMR (200 MHz, CDCl3 þ DMSO-d6), ꢀ:
1
8.46 (1H, s), 8.24 (1H, dd, J ¼ 8.795, 1.99, 1.95), 7.19 (1H, d, J ¼ 8.79),
4.05 (3H, s). EI-MS m/z 197 (Mþ).
ACKNOWLEDGMENTS
The author, Ganesh Y. S. S. and Madhavi, A. V. are thankful to the
Council of Scientific and Industrial Research (CSIR) for the financial
support in the form of fellowship.

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Clay Supported Ammonium Nitrate
REFERENCES
2503
1. (a) Olah, G.A.; Malhotra, R.; Narang, S.C. Nitration Methods and
Mechanisms; VCH Publications: New York, 1989; (b) Schofield, K.
Aromatic Nitration; Cambridge University Press: Cambridge, 1980.
2. Meshram, H.M.; Reddy, G.S.; Yadav, J.S. Tetrahedron Lett. 1997,
38, 8891; (b) Yadav, J.S.; Meshram, H.M.; Reddy, G.S.; Sumithra, G.
Tetrahedron Lett. 1998, 39, 3043.
3. Clayan is prepared following the earlier procedure: To a solution of
ammonium nitrate (5 g) in distilled water (70 mL) was added mont-
morillonite K10 (Aldrich Chemical Co.) 5 g in portions at room tem-
perature and the suspension stirred for 1 h. water is removed using
rotary evaporator at 50–60ꢀC under reduced pressure and thew
resulting solid was dried under vacuum at 40ꢀC for 2 h and the
reagent stored in a stoppered bottle. Detailed experimental procedure
may be obtained from the Indian patent No: 56/Del/99.
4. Bosch, E.; Kochi, J.K. J. Org. Chem. 1994, 59, 5573 and the
references cited therein.
5. Riego, J.M.; Sedin, Z.; Zaldivar, J.M.; Marziano, N.C.; Tortato, C.
Tetrahedron Lett. 1996, 37, 4, 513.
6. (a)Koga, H.; Sato, H. Jpn. Kokai. Tokkyo, Koho. JP07, 196, 635. [95,
196, 635] cl. (07d265/16). Chem. Abstr. 1995, 123, 340163a; (b)
Komura, H.; Ueda, K. Jpn. Kokai. Tokkyo, Koho. JP 01 09, 980
[89, 09, 980] cl (07d265/26). Chem. Abstr. 1989, 111, 57742h.
7. (a) Lee, B.S.; Chung, K.H.; Kim, U. J. Korean Chem. Soc. 1996, 40,
457; (b) Mishra, T.; Parida, K.M. J. Mol. Catal. A: Chem. 1997,
121, 91; (c) Parida, K.M.; Pattnayak, P.K. Catal. Lett. 1997, 47, 255.
8. (a) Coombes, R.G. Comprehensive Organic Chemistry; Sir Barton,
D.F.R.S. Ed.; Pergamon Press: Oxford, 1979; Vol. 2, 305–381.
9. (a) Griffiths, P.H.; Walkey, W.A.; Watson, H.B. J. Chem. Soc.
1934, 631; (b) Halvarson, K.; Melkander, L. Arkiv. Kemi 1957,
11, 77; (c) Hooleman, A.F.; Hartogs, J.C.; Vander, L.T. Ber. 1911,
44, 704; (d) Arnall, F. J. Soc. Chem. Ind. 1929, 48, 157; (e) Laszlo,
P.; Pennetreau, P. J. Org. Chem. 1987, 52, 2407.
10. (a) Dictionary of Organic Compounds, 6th Ed.; Chapmann & Hall:
London, 1996; (b) Walker, G.N. J. Am. Chem. Soc. 1955, 77, 3844;
Bosch, E.; Kochi, J.K. J. Org. Chem. 1994, 59, 5573 and the
references cited therein; (c) Cain, J.C.; Simonsen, J.L. J. Chem.
Soc. 1914, 105, 156; (d) Gomberg, M.; Bachmann, W.E. J. Am.
Chem. Soc. 1924, 46, 2339.
Received in the Netherlands November 14, 2002

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