Nitration of phenolic compounds by antimony nitrate

Article abstract of DOI:10.1080/15533174.2011.555861

Antimony nitrate is new compound to be an efficient nitration reagent in the nitration of phenolic compounds with high yields. This producerworks efficiently onmost of the examples, as a grinding nitration reaction, proceed very fast (～1 min) and thermogenic. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.555861

This article was downloaded by: [Florida Atlantic University]
On: 10 August 2013, At: 11:00
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
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
Nitration of Phenolic Compounds by Antimony
Nitrate
a
b
Hassan Fathinejad Jirandehi & Marjan Mirzaeian
a
Chemistry Department, Islamic Azad University, Farahan Branch, Farahan, I. R. Iran
Chemistry Department, Arak University, Arak, I. R. Iran
b
Published online: 12 Apr 2011.
To cite this article: Hassan Fathinejad Jirandehi & Marjan Mirzaeian (2011) Nitration of Phenolic Compounds by Antimony
Nitrate, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:3, 284-286
To link to this article: http://dx.doi.org/10.1080/15533174.2011.555861
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

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:284–286, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.555861
Nitration of Phenolic Compounds by Antimony Nitrate
1
2
Hassan Fathinejad Jirandehi and Marjan Mirzaeian
1
Chemistry Department, Islamic Azad University, Farahan Branch, Farahan, I. R. Iran
Chemistry Department, Arak University, Arak, I. R. Iran
2
EXPERIMENTAL SECTION
Antimony nitrate is new compound to be an efficient nitration
All chemicals were of reagent grade quality and used with-
out further purification. Melting points were measured by Dig-
ital Melting Point Apparatus. IR spectra were performed on a
reagent in the nitration of phenolic compounds with high yields.
This producer works efficiently on most of the examples, as a grind-
ing nitration reaction, proceed very fast (∼1 min) and thermogenic.
1
Galaxy FT-IR 500 spectrophotometer. H NMR spectra were
recorded on a Brucker 300 MHz spectrometer. Reactions were
monitored by thin layer chromatography using silica gel F254
aluminum sheets (Merck). All materials were used as obtained
without further purification.
Keywords catalyst, grinding, nitration, nitrophenols, phenol
INTRODUCTION
The nitration reaction in chemistry may be done with many Catalyst Preparation
nitrating reagents. In organic chemistry, nitro compounds are
New catalyst, Sb(NO ) .5H O, was obtained from adding
3
3
2
◦
organic compounds that contain one or more nitro functional nitric acid to metallic antimony (Sb), then dried at 80 C tem-
groups. In traditional method, a mixture of concentrated nitric peratures. Antimony nitrate had been employed as a catalyst in
acid and sulfuric acid has been used as the most common ni- the nitration of phenolic compounds.
trating reagent for the nitration of benzene, alkylbenzene, and
less reactive aromatic compounds,[1] particularly easily oxidized
General Procedure
[
2−4]
substances such as aniline, phenols, pyroles, etc.
Since ni-
1.0 mmol of catalyst to 1.0 mmol of phenolic compound (or
trophenoles are very important organic synthetic intermediates,
it is still an interesting subject of organic synthesis to develop
the nitrating procedures. Nitration of phenolic compounds as a
special reaction has been studied using various nitrating agents
under different conditions and is a very useful method in or-
ganic synthesis that their find use in many industrial application.
The recent development of nitration of phenolic compounds
together with wet SiO2) in beaker 25 mL added in cold water
bath. After grinding mixture for some seconds, the reaction was
carried out with release gas and heated. After time (1 min),
crude product formed and tried to purify it by acetone or ethylic
alcohol.
2
a) 2,6-dinitro-4-methylphenol
[5]
[6]
using nitrate salts such as VO (NO3)3, Fe (NO3)3.9H2O,
◦
mp: 76–78 C, yield 92%. IR (KBr): 3493(OH), 3059(CHarom),
7]
[8]
(
Me4N)NO,[ Mg(NO3)2·2H2O, and NaNO2[9] as the nitrat-
−1
1
2
924 (CHaliph), 1624 (C=C), 1516, 1365 (NO2) cm . H NMR
ing reagent has been reported. However, the reported nitration
(
DMSO-d6): δ = 2.33 (s, 3H, CH3), 8.08(s, 2H, CHarom) ppm.
C NMR (DMSO-d6): δ = 19 (CH3), 129 (C=C), 130 (C=C),
40 (C=C), 144 (C=C) ppm.
by using nitrate salt as nitrating reagents required either special 13
solvents or co-reagents. Bi(NO3)3 had been employed as a co-
1
catalyst in the nitration of phenolic compounds with 65% nitric
acid,[ and as a nitrating reagent of aromatic compounds cat-
10]
2
b) 4-nitro-1-naphthol
[
11]
alyzed by montmorillonite KSF.
Bi (NO3)3.5 H2O was used
◦
mp: 164–167 C IR (KBr): 3420 (OH), 3084 (CHarom), 1613
as an efficient catalyst in the nitration of phenolic compounds.[
12]
−1
1
(
(
C=C), 1585.95 (NO2), 1327.11 (NO2) cm
.
H NMR
DMSO-d6): δ = 7.09–8.94 (m, 6H, CHarom), 9.09 (s, 1H,
OH)ppm
2
c)2,6-dinitro-4-flourolphenol
Received 30 May 2010; accepted 7 September 2010.
Address correspondence to Hassan Fathinejad Jirandehi, Chemistry
Department, Islamic Azad University, Farahan Branch, Farahan, I. R.
Iran. E-mail: hfathinejad@iau-farahan.ac.ir
◦
mp: 60–63 C IR (KBr): 3415 (w,OH), 3171, 3099 (CHarom),
−1
−1
1
1
604.88 (C=C) cm , 1550 ( NO2), 1357.93 (NO2) cm . H
NMR (DMSO-d6): δ = 8.26 (s, 2H, CHarom) ppm. 13C NMR
284

CATALYTICAL SYNTHESIS OF ORGANIC COMPOUNDS
285
TABLE 1
Nitration of phenolic compounds
Compound
Yield(%)
Compound
Yield(%)
OH
OH
O N
NO2
O N
NO2
2
2
9
1
90
Cl
CH3
2
f
2
a
OH
OH
OHC
6
5
82
NO2
NO2
2
b
2
g
NO2
OH
OH
O N
NO2
2
9
0
8
0
F
2h
2
c
OH
OH
H C
CH3
Cl
Cl
3
8
5
NO2
NO2
8
8
2
i
2
d
OH
NO2
O N
CH3
OH
2
HO
8
5
95
CH3
2
e
2j

286
H. F. JIRANDEHI AND M. MIRZAEIAN
2
j) 2-nitroresorcinol
OH
OH
◦
mp: 78–82 C yield 95%. IR (KBr): 3195 (w, OH), 3078
Sb(NO ) .nH O
−1
1
3
3
2
(
CHarom), 1603 (C=C), 1556 (NO2), 1345 (NO2) cm . H
NO2
NMR (DMSO-d6): δ = 6.93–7.23 (m, 3H, CHarom) ppm.
G
G
RESULT
SCH. 1.
In this article, we reported the result of the investigation on
(
(
DMSO-d6): δ = 117 (C=C), 140 (C=C), 143 (C=C), 153 the nitration of phenolic compounds using Sb(NO3)3.5H2O as a
C=C) ppm.
nitrating reagent in the solid phase both alone and together with
wet SiO2 (Scheme 1). This reaction proceeded very fast (∼1
min) and exothermic. For control of reaction temperature, we
2
d) 2,6-dichloro 4-nitrophenol
◦
mp: 123–125 C IR (KBr): 3385 (OH), 3090 (CHarom), 1619 used cold water container as sinker of reaction beaker. Reaction
−1 1
(
C=C), 1529 ( NO2), 1329 ( NO2) cm . H NMR (DMSO- time and yield result showed antimony nitrate can do nitration
13
d6): δ = 8.20 (s, 2H, CHarom) C NMR (DMSO-d6): δ = 122 reaction faster of all catalyst used until now. Advantage of this
(
C=C), 124 (C=C), 139 (C=C), 156 (C=C) ppm.
work is reaction high rate (∼1 min) and high yields (Table 1).
Usage of wet SiO2 together with catalyst as supporting is very
1
2e) 2,4-dimethyl-6-nitrophenol
good for purification of production. As seen in H NMR data,
◦
the spectrum of OH is not appeared for some nitro compounds
because has OH high acidity.
mp: 162–165 C IR (KBr): 3321 (OH), 3128.12 (CHarom),3012
−
1
(
CHarom), 1592.52 (C=C) cm , 1530.14 (NO2), 1326 (NO2)
−1 1
cm . H NMR (DMSO-d6): δ = 2.12 (s, 6H, CH3), 7.01 (m,
1
H, CHarom), 7.62 (m, 1H, CHarom), 11.56 (bs, 1H, OH) ppm
REFERENCES
1
. (a) Schofield, K. Aromatic Nitration; Cambridge University Press: Cam-
bridge, 1980. (b) Olah, G.S.; Malhotra, R.; Narang, S.C. Nitration: Methods
and Mechanism; VCH Publishers: New York, 1989. (c) Ridd, J. H. Chem.
Soc. Rev. 1991, 20, 149–156
4
f)4-chloro-2,6-dinitophenol
◦
mp: 171–173 C IR (KBr): 3153 (OH), 3012 (CHarom), 1613.32
−1
1
(
C=C), 1514.23 (NO2), 1326.41 (NO2) cm
.
H NMR
2
. (a) Gigante, B.; Prazeres, A.O.; Marcello-Curto, M.J.; Corenelis, A.; Las-
zlo, P. J. Org. Chem. 1995, 60, 3445–3447. (b) Rodringnes, J.A.R.; Filho,
A.P. de Oliveira; Moran, P.J.S.; Custodio, R. Tetrahedron 1999, 55, 3733–
6738.
(DMSO-d6): δ = 7.99 (s, 2H, CHarom), 9.35 (bs, 1H, OH) ppm.
2
g) 2-hydroxy-5-nitrobenzaldehyde
◦
3. Iranpoor, N.; Firouzabadi, H.; Heydari, R. Synths. Commun.; 1999, 29,
295–3302.
. Iranpoor, N.;Firouzabadi, H.; Heydari, R. Synths. Commun.; 2003, 33, 703–
10.
mp: 124–127 C IR (KBr): 3286 (OH), 3078 (CHarom), 1710
3
−1
(
C=O) cm , 16.12.24 (C=C), 1524 (NO2), 1362.25 (NO2)
4
−1 1
cm . H NMR (DMSO-d6): δ = 6.95 (m, 1H, CHarom),7.26
m, 1H, CHarom), 9.129 (bs, 1H, OH), 10.23 (s, 1H, CHO) ppm.
7
(
5. Dove, M.F.A.; Manz, B. Montgomery, J.; Patterndon, G.; Wood, S.A.J.
Chem. Soc., Perkin Trance. 1 1998, 1589–1590.
6
. Rajagopal, R.; Srinivasan, K.V. Synth. Commun. 2003, 33, 961–
66.
2
h) 1-nitro-2-naphthol
9
◦
mp: 121–123 C yield 92%. IR (KBr): 3246 (OH), 3012
7
. Schackelford, S.A.; Anderson, M.B.; Christie, L.C.; Geotzen, T.; Guz-
man, M.C.; Hananel, M.A.; Korreich, W.D.; Li, H.; Pathak, V.P.; Rabi-
novich, A.K.; Rajapakse, R.J.; Truesdale, L.K.; Tsank, S.M.; Vazir, H.N. J.
Org.Chem. 2003, 68, 267–275.
−1
−1
.
(
CHarom), 1593 (C=C) cm , 1516 (NO2), 1340 (NO2) cm
1
H NMR (DMSO-d6): δ = 7.07–7.99 (m, 7H, CHarom), 8.01 (d,
1
H, OH) ppm.
8. Zolfigol, M.A.; Ghaemi, E.; Madrakian, E. Synth. Commun. 2000, 30, 1689–
1
694.
2
j) 2,6-dimethyl-4-nitrophenol
9
. (a)Zolfigol, M. A.; Ghaemi, E.; Madrakian, E. Molecules 2001, 6, 614–
620.(b) Zolfigol, M. A.; Ghaemi, E.; Madrakian, E. Synlett 2003, 191–194.
(c) Zolfigol, M. A.; Ghaemi, E.; Madrakian, E. Molecules 2002, 7, 734–
◦
mp: 162–165 C yield 92%. IR (KBr): 3252 (w,OH), 3078
−1 1
(
CHarom), 2951 (CHaliph), 1613 (C=C) cm . H NMR (DMSO-
d6): δ = 2.06 (s, 6H, CH3),7.10 (s, 1 H, OH), 8.16 (s, 2H, CHarom)
ppm. C NMR (DMSO-d6): δ =122 (C=C), 124 (C=C), 139
7
41.
1
1
0. Shi, M.; Cui, S.C. Adv. Synth. Catal. 2003, 345, 1197–1202.
1. Samajdar, S.; Becker, F.F.; Banik, B.K. Tetrahderon Lett. 2000, 41, 8017–
8
13
13
(
1
C=C),156 (C=C) ppm. C NMR (DMSO-d6): δ = 17 (CH3),
24 (C=C), 126 (C=C), 131 (C=C), 152 (C=C) ppm.
020.
12. Sun, H.; Hua,R.; Yin,Yi. J. Org. Chem. 2005, 70, 9071–9073.