A simple approach for preparation of dinitronaphthalene compounds from the nitration reaction of 1-nitronaphthalene with NO2 as nitration reagent

Article abstract of DOI:10.1007/s11164-014-1893-1

A simple method for the preparation of dinitronaphthalene from the nitration reaction of 1-nitronaphthalene with NO₂ as nitration reagent under the mild conditions has been successfully developed in this work. The results indicated that Ni(CH₃COO)₂·4H₂O catalyst shows better catalytic performances, and the conversion of 1-nitronaphthalene is 33.10 % with 34.10, 23.56, 19.30, and 3.56 % of the selectivity to 1,5-DNN, 1,3-DNN, 1,4-DNN, and 1,8-DNN, respectively, under the optimal reaction conditions. This is a mild, environmentally benign, and economical method for the preparation of dinitronaphthalene.

Full text of DOI:10.1007/s11164-014-1893-1

Res Chem Intermed
DOI 10.1007/s11164-014-1893-1
A simple approach for preparation
of dinitronaphthalene compounds from
the nitration reaction of 1-nitronaphthalene
with NO as nitration reagent
2
Kuiyi You
Renjie Deng
•
Zhongcang Zhou
•
•
Jian Jian
•
•
Pingle Liu Qiuhong Ai
•
He’an Luo
Received: 12 September 2014 / Accepted: 9 December 2014
Ó Springer Science+Business Media Dordrecht 2015
Abstract A simple method for the preparation of dinitronaphthalene from the
nitration reaction of 1-nitronaphthalene with NO as nitration reagent under the mild
conditions has been successfully developed in this work. The results indicated that
2
Ni(CH COO) ꢀ4H O catalyst shows better catalytic performances, and the con-
3
2
2
version of 1-nitronaphthalene is 33.10 % with 34.10, 23.56, 19.30, and 3.56 % of
the selectivity to 1,5-DNN, 1,3-DNN, 1,4-DNN, and 1,8-DNN, respectively, under
the optimal reaction conditions. This is a mild, environmentally benign, and eco-
nomical method for the preparation of dinitronaphthalene.
Keywords Preparation ꢀ Dinitronaphthalene ꢀ 1-Nitronaphthalene ꢀ NO2 ꢀ
Nitration
Introduction
The preparation of nitro-compounds from the nitration of aromatic compounds is an
important industrial process. Dinitronaphthalene compounds can be obtained by the
nitration of naphthalene. Dinitronaphthalene compounds are important chemical
materials that are widely used in polyurethane, dyes, and organic intermediates. For
example, 1,5-dinitronaphthalene (1,5-DNN) can be used to produce 1,5-naphthalene
K. You ꢀ Z. Zhou ꢀ J. Jian ꢀ R. Deng ꢀ P. Liu ꢀ Q. Ai ꢀ H. Luo
School of Chemical Engineering, Xiangtan University, Xiangtan 411105,
People’s Republic of China
K. You (&) ꢀ P. Liu ꢀ Q. Ai ꢀ H. Luo (&)
National and Local United Engineering Research Center for Chemical Process Simulation
and Intensification, Xiangtan University, Xiangtan 411105, People’s Republic of China
e-mail: youkuiyi@126.com
H. Luo
e-mail: heanluo@126.com
123

K. You et al.
diisocyanate (NDI), which is an important raw material for the production of
advanced polyurethane with perfect performances of high hardness, excellent
elasticity, low compression set, heat resistance, good dynamic capability, and wear
resistance [1, 2]. 1,3-dinitronaphthalene (1,3-DNN) [3] can be used for the sensitizer
of ammonium nitrate explosive, carbide additive, and sulfur dyes intermediate.
1
,4-dinitronaphthalene (1,4-DNN) [4] is also a very important organic synthesis
intermediate, and 1,8-dinitronaphthalene (1,8-DNN) can be widely applied for the
production of dyes [5].
The preparations of these dinitronaphthalene compounds are mainly achieved by
traditional nitration processes involving large quantities of nitric acid and sulfuric
acid. However, these processes suffer many serious disadvantages, including low
selectivity, generation of large quantities of corrosive waste acids and oxidative
degradation byproducts, inefficient atomic economy, and expensive processing cost.
For example, the yield of 1,5-DNN is only approximately 25–30 %, whereas yields
of 1,8-DNN and 1-nitronaphthalene are approximately 60 and 10 % [6], respec-
tively. Therefore, the development of a green, simple, and environmentally benign
process for the selective synthesis of desired isomer in the liquid phase nitration of
aromatic compounds is urgently desirable from both synthetic and industrial points
of view.
In order to overcome the above-mentioned problems, some methods for the
nitration of 1-nitronaphthalene or naphthalene to dinitronaphthalene in nitric acid
have been reported. Barbara Gigante et al. [7] used acidic montmorillonite clay
impregnated with anhydrous cupric nitrate for the nitration of naphthalene
with fuming nitric acid under the mild conditions, and selectivities of 1,8-DNN,
1
,5-DNN, 1,6-DNN, and 1,7-DNN are 70, 23, 4, and 3 %, respectively. Some
researchers reported that the dinitronaphthalene can be prepared from the nitration
reaction of nitronaphthalene [8], or naphthalene [9] with nitric acid. Although these
methods can reduce the waste acid, they can not improve remarkably the proportion
of 1,5-DNN to 1,8-DNN. Solid acid and ionic liquid catalysts have been used for the
nitration of naphthalene or other aromatic compounds [10–14]. However, the
selectivity of 1,5-DNN in the catalytic nitration of naphthalene is only approxi-
mately 30–40 %, and 1,8-DNN is still the main product. Hence, there are many
attempts to improve the selectivity of 1,5-DNN by using other catalysts, especially
zeolites for their shape-selective behavior. Brandt Matthias et al. [15] have found
that the zeolite catalyst is effective for the nitration reaction of 1-nitronaphthalene
with nitric acid, which gives 57.9 % of selectivity to 1,5-DNN. Liu et al. [16] have
reported that nitration of naphthalene with nitric acid over a zeolite-supported
phosphotungstic acid catalyst, the selectivity of 1,5-DNN can reach 48.5 % under
the optimal reaction conditions.
Recently, nitrogen dioxide (NO ) as an environmentally friendly nitration
2
reagent instead of nitric acid has attracted much attention [17, 18]. Peng et al.
[
19–21] have reported the synthesis approach of 1,5-DNN and 1,8-DNN from the
nitration of 1-nitronaphthalene or naphthalene with nitrogen dioxide as nitrating
reagent. The goal of the present investigation was to develop a mild, easy-to-operate
without involving sulfuric acid or nitric acid.
1
23

Preparation of dinitronaphthalene compounds
In this paper, we report the nitration of naphthalene and 1-nitronaphthalene with
nitrogen dioxide without the use of nitric acid/sulfuric acid or nitric acid (see
Scheme 1). The yield of 1-nitronaphthalene can be over 95 %, and two useful
dinitronaphthalene products (1,3-DNN and 1,4-DNN) were obtained in this system.
This method can improve the proportion of 1,5-DNN to 1,8-DNN and it is a
mild, environmentally benign, and economical method for the preparation of
dinitronaphthalene.
Experimental
Reagents and instrument
Naphthalene (AR) was purchased from Aladdin Industrial Corporation. NO (purity
2
[99.9 %) was purchased from Beijing Chemical Co., Ltd., China. Except where
specified, all chemicals were of analytical grade and used as received. Gas
chromatography was performed on an Agilent 7890 equipped with a DB-5 (30 m 9
0
.25 mm 9 0.25 lm) column and hydrogen flame ionization detector (FID) for
quantitative analysis by using internal standard method. Gas chromatography-mass
spectrometry (GC–MS) was run on a Shimadzu GCMS-QP2010 PLUS for
qualitative analysis.
Typical experimental procedure
The nitration reaction of naphthalene and 1-nitronaphthalene with NO2 was
performed in a 100-ml reaction autoclave with magnetic stirrer and temperature-
control device. Firstly, 1-nitronaphthalene (10 mmol), acetonitrile solvent (20 ml),
cold liquid nitrogen dioxide (20 mmol), and catalyst (0.2 g) were added in a sealed
NO2
1,3-DNN
NO2
NO2
1
,4-DNN
NO2
NO2
NO2
NO2
NO2
catalyst
(
yield 95%)
1,5-DNN
NO2
NO2 NO2
1,8-DNN
Scheme 1 Regioselective synthesis of dinitronaphthalene compounds from the nitration of
-nitronaphthalene with nitrogen dioxide as nitration reagent
1
123

K. You et al.
autoclave. The autoclave was immersed in an oil bath maintained at a pre-selected
temperature. Then, the reaction mixture was stirred at 100 °C for 3 h. After cooling
to room temperature, the resulting reaction mixture was fully dissolved in
acetonitrile and the catalyst was separated by filtration. The obtained reaction
liquid was analyzed by GC and GC–MS.
The qualitative analysis of products
All nitration reaction products were analyzed by GC–MS. The results indicated that
the nitration products of naphthalene with NO were mainly 1-nitronaphthalene
2
(
yield[95 %) and a small amount of 2-nitronaphthalene. The nitration products of
-naphthalene with NO were mainly 1,5-DNN, 1,3-DNN, 1,4-DNN, and 1,8-DNN
1
2
in present system. In addition, the small amounts of 1,6-DNN, 1,7-DNN,
trinitronaphthalene, and oxidation product phthalic acid were also detected in the
different reaction conditions.
Results and discussion
Effects of reaction temperature on the nitration reaction of 1-nitronaphthalene
with NO2
The effects of reaction temperature on the conversion of 1-nitronaphthalene and the
selectivity to dinitronaphthalene isomers were investigated in the nitration reaction,
and the results are illustrated in Fig. 1. It is clearly found that there is significant
influence of reaction temperature on the conversion and selectivity. The conversion
of 1-nitronaphthalene increased rapidly from 3.6 to 41.5 % when the reaction
4
4
3
3
2
2
1
1
5
0
5
0
5
0
5
0
Conversion of 1-nitronaphthalene
Selectivity to 1,4-DNN
Selectivity to 1,5-DNN
Selectivity to 1,3-DNN
Selectivity to 1,8-DNN
5
0
4
0
60
80
100
120
140
160
o
Reaction temperature ( C)
Fig. 1 Effects of reaction temperature on the nitration reaction of 1-nitronaphthalene with NO
2
. Reaction
conditions: the molar ratio of 1-nitronaphthalene to NO : 1:2, reaction time: 3 h, solvent: acetonitrile
2
1
23

Preparation of dinitronaphthalene compounds
temperature was elevated from 50 to 150 °C. The selectivity of 1,5-DNN increased
first and slightly decreased afterwards, while the selectivity of 1,3-DNN, 1,4-DNN,
and 1,8-DNN showed a declining trend with elevated temperature. Maybe a
relatively high reaction temperature is beneficial to the formation of 1,5-DNN.
There are some possible reasons for this phenomenon. There are competitive and
consecutive reactions in this nitration process of 1-nitronaphthalene with NO2.
Higher reaction temperature accelerated the formation of dinitronaphthalene to
trinitronaphthalene. Especially the selectivity of 1,4-DNN declined obviously while
the selectivity of 1,3-DNN and 1,8-DNN changed insignificantly when the reaction
temperature was elevated. Therefore, a range of favorable reaction temperature was
about 100 °C from the point of the conversion of 1-dinitronaphthalene and the
selectivity of 1,5-DNN. These results indicated that the reaction temperature was a
significant factor in regulating the selectivity of products from the nitration reaction
of 1-nitronaphthalene with NO2.
Effects of molar ratio of 1-nitronaphthalene to NO on the nitration reaction
2
Table 1 summarizes the representative results for the effects of molar ratio of
1
of 1-nitronaphthalene increases rapidly with raising the concentration of NO , and
-nitronaphthalene to NO on nitration reaction. It can be seen that the conversion
2
2
the selectivity of 1,5-DNN, 1,3-DNN, and 1,8-DNN seems to decline, while the
selectivity of 1,4-DNN increases marginally with raising concentration of NO2.
From the points of the conversion and the selectivity, it is clearly found that the
favorable molar ratio of 1-nitronaphthalene to NO is selected at 1:2 under the
2
reaction temperature of 100 °C and the reaction time of 3 h. The good result that
3
0.70 % of conversion with 24.86 % of selectivity to 1,5-DNN and 25.96 % of
selectivity to 1,3-DNN was obtained in the nitration reaction of 1-nitronaphthalene
and NO2.
Effects of reaction time on the nitration reaction of 1-nitronaphthalene with NO2
Figure 2 reveals the effects of reaction time on nitration reaction under the reaction
temperature of 100 °C and the molar ratio of 1-nitronaphthalene to NO is 1:2. It
2
a
Table 1 Effects of molar ratio of 1-nitronaphthalene to NO
2
on nitration reaction
Selectivity (%)
,4-DNN
Molar ratio
2
1-nitronapthalene:NO )
Conversion (%)
(
1
1,5-DNN
1,3-DNN
1,8-DNN
1
1
1
1
1
a
:1
:2
:3
:4
:5
15.17
30.70
41.66
64.64
77.86
3.89
5.05
5.27
6.14
6.54
25.23
24.86
22.00
21.06
20.43
24.69
25.96
24.08
23.71
22.23
5.60
3.64
3.66
2.83
2.51
Reaction conditions: reaction temperature: 100 °C, reaction time is 3 h, solvent: acetonitrile
123

K. You et al.
50
40
30
20
10
0
Conversion of 1-nitronaphthalene
Selectivity to 1,4-DNN
Selectivity to 1,5-DNN
Selectivity to 1,3-DNN
Selectivity to 1,8-DNN
0
5
10
15
20
25
Reaction time (h)
Fig. 2 Effects of reaction time on the nitration reaction of 1-nitronaphthalene with NO . Reaction
: 1:2, reaction temperature: 100 °C, solvent:
2
conditions: the molar ratio of 1-nitronaphthalene to NO
acetonitrile
2
can be seen that the conversion of 1-nitronaphthalene increases rapidly with
prolonged reaction time in the first 6 h, while the selectivity to 1,5-DNN first
increases and then decreases slightly, the selectivity to 1,3-DNN, 1,4-DNN and
1
,8-DNN decreases slightly with reaction time. A possible reason is that long
reaction times lead the formed dinitronaphthalene to trinitronaphthalene. From the
points of the conversion and the selectivity, a suitable reaction time is 3 h.
Therefore, from the single-factor experiment results, the optimal reaction
conditions were obtained that the reaction temperature was 100 °C, reaction time
was 3 h, and the molar ratio of 1-nitronaphthalene to NO was 1:2 in the nitration
2
reaction of 1-nitronaphthalene with NO . The results indicated that the conversion
2
of 1-nitronaphthalene is 30.70 % and the selectivity to 1,5-DNN, 1,3-DNN,
1
,4-DNN, and 1,8-DNN is 24.86, 25.96, 5.05, and 3.64 %, respectively.
Effects of different catalysts on nitration reaction of 1-nitronaphthalene
with NO2
Table 2 summarizes representative results for the nitration reaction of 1-nitronaph-
thalene with NO over various catalysts. The selectivity of 1,4-DNN and 1,5-DNN
2
was relatively low, especially the selectivity to 1,4-DNN was only 5.05 % with
3
0.70 % of conversion in the absence of any catalysts. In this catalytic system, the
catalytic performances of the present catalysts were different. Most of the
researched catalysts could improve the selectivity of 1,5-DNN and 1,4-DNN.
The selectivity to 1,5-DNN was only 24.86 % with 30.70 % of conversion in the
absence of any catalysts, and the conversion of 1-nitronaphthalene and the
selectivity of 1,5-DNN and 1,4-DNN were obviously improved when catalysts were
introduced to the reaction system. Moreover, the ratio of 1,3-DNN to 1,4-DNN was
1
23

Preparation of dinitronaphthalene compounds
a
2
Table 2 Effects of different catalysts on nitration reaction of 1-nitronaphthalene with NO
Catalysts
Conversion (%)
Selectivity (%)
1
,4-DNN
1,5-DNN
1,3-DNN
1,8-DNN
None
30.70
40.18
37.34
33.10
39.68
44.07
5.05
24.86
29.02
30.32
34.10
30.75
29.57
25.96
22.40
23.35
23.56
22.48
22.86
3.64
2.68
3.02
3.56
2.89
2.90
Ni-AlVPO
17.03
16.18
19.30
16.29
13.82
Mg(NO
Ni(CH COO)
NiSO
3
)
2
ꢀ6H
2
O
3
2
ꢀ4H
2
O
4
ꢀ6H
2
O
Na-ZSM-5
a
2
Reaction conditions: the molar ratio of 1-nitronaphthalene to NO : 1:2, reaction time: 3 h, reaction
temperature: 100 °C, catalyst: 0.2 g
close to 5.0 in the absence of catalysts. However, the selectivity to 1,4-DNN was
obviously improved under the action of catalysts, and the ratio of 1,3-DNN to
1,4-DNN was only about 1.5. The possible reason for this was that the 1,4-DNN was
easily formed in contrast to 1,3-DNN in the presence of catalysts. Among these
catalysts, the Ni(CH COO) ꢀ4H O catalyst gave the best results with 33.10 % of
3
2
2
conversion and 34.10, 19.30, and 23.56 % of selectivity to 1,5-DNN, 1,4-DNN,
1
1
,3-DNN, respectively. Further studies for the catalytic nitration reaction of
-nitronaphthalene with NO are now in progress.
2
The possible nitration reaction mechanism of 1-nitronaphthalene with NO2
As is known, the traditional mixed-acid nitration reaction mechanism of aromatic
?
hydrocarbon is the electrophilic mechanism of nitronium ion (NO2 ), and Pryor
et al. [22] report multi-step, radical addition–elimination mechanisms that explain
the formation of the observed products from the reaction of naphthalene and
2
similar mechanism for the nitration of 1-nitronaphthalene with NO . The possible
-nitronaphthalene with NO . On the basis of the results in this work, we proposed a
2
2
formation pathway of dinitronaphthalene from the nitration reaction of 1-nitro-
naphthalene with NO is suggested in Scheme 2, and the proposed formation
2
pathway of dinitronaphthalenes may be the radical reaction mechanism according to
the obtained dinitronaphthalene products and the reported nitration mechanism by
Pryor et al. Presumably, the nitration of 1-nitronaphthalene with NO maybe has
2
three possible reaction pathways. 1,4-DNN and 1,3-DNN can be obtained from the
path I, 1,5-DNN and 1,6-DNN may be obtained from the path II and 1,8-DNN and
1
1
,7-DNN may be obtained from the path III. Furthermore, the ratio of 1,3-DNN to
,4-DNN was obviously different, and the selectivity to 1,4-DNN was obviously
improved under the action of catalysts from the obtained results in Table 2. The
0
possible reason for this was that 3 -HONO on the intermediate was easily
eliminated, thus the 1,4-DNN was easily formed in contrast to 1,3-DNN in the
presence of catalysts.
123

K. You et al.
NO2
H
NO2
H
NO2
NO2
NO2
-
HONO
NO2
H
+
H
NO2
I
2
O N
O2N
NO2
1, 4-DNN
th
a
p
1, 3-DNN
NO2
NO2
path III
NO2
NO2
NO2
NO2
path II
NO2
-HONO
-HONO
O2N
+
O2N
H
H
path II
path I
NO2
H
NO2
NO2
H
NO2
NO2
NO2
1, 5-DNN
1, 6-DNN
NO2
p
NO2
ath I
I
I
O N
2
H
O N
H
NO2 NO2
2
H
H
2
O N
NO2
O2N
+
1
, 8-DNN
1, 7-DNN
Scheme 2 Possible reaction path of 1-nitronaphthalene with NO
2
Conclusions
In conclusion, we have developed a simple method for regioselective preparation of
dinitronaphthalene compounds from the nitration reaction of 1-nitronaphthalene
with NO2 as nitration reagent in the present work. The effects of reaction
temperature, reaction time, the molar ratio of 1-nitronaphthalene to NO , and
2
catalyst on the nitration reaction were examined. The results indicate that 33.10 %
of conversion with 34.10, 19.30, and 23.56 % of selectivity to 1,5-DNN, 1,4-DNN,
1
,3-DNN, respectively, was obtained over Ni(CH COO) ꢀ4H O catalyst, and the
3
2
2
total selectivity for 1,5-DNN, 1,4-DNN, 1,3-DNN, and 1,8-DNN was over 80 %
under optimal reaction conditions. Further studies for the catalytic nitration reaction
are now in progress. Assuming that better catalysts can be developed, it provides a
new method for the preparation of dinitronaphthalenes, especially obtaining a high
proportion of 1,5-DNN to 1,8-DNN from the nitration reaction of 1-nitronaphtha-
lene with NO as nitration reagent.
2
Acknowledgments The authors are grateful for the financial support for this work by the National
Natural Science Foundation of China (21276216), Specialized Research Fund for the Doctoral Program of
Higher Education (20124301130001), Scientific Research Fund of Hunan Provincial Education
Department (13A096) and Major Science and Technology Projects of Hunan Province (2012FJ1001).
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