Kinetics of oxidative ammonolysis of 4-bromo-o-xylene: V. Synthesis of 4-bromophthalonitrile

Article abstract of DOI:10.1134/S107036321406005X

Oxidative ammonolysis of 4-bromo-o-xylene on a V-Sb-Bi-Zr/γ-Al ₂O₃ catalyst gives 74.82 mol % of 4-bromophthalonitrile at a high conversion of the starting xylene in a one-cycle process. The process with recirculation results in decreased number of by-products and contribution of deep oxidation and increased selectivity in 4-bromophthalonitrile up to 95.42-96.58%.

Full text of DOI:10.1134/S107036321406005X

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 6, pp. 1085–1090. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © G.A. Bagirzade, D.B. Tagiev, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 6, pp. 902–907.
Kinetics of Oxidative Ammonolysis of 4-Bromo-о-xylene:
V.1 Synthesis of 4-Bromophthalonitrile
G. A. Bagirzadea and D. B. Tagievb
a Nagiev Institute of Chemical Problems, National Academy of Sciences of Azerbaijan,
pr. G. Dzhavida 29, Baku, Az1143 Azerbaijan
e-mail: iradam@rambler.ru
b Azerbaijan Medical University, Baku, Azerbaijan
Received August 29, 2013
Abstract—Oxidative ammonolysis of 4-bromo-о-xylene on a V–Sb–Bi–Zr/γ-Al2O3 catalyst gives 74.82 mol %
of 4-bromophthalonitrile at a high conversion of the starting xylene in a one-cycle process. The process with
recirculation results in decreased number of by-products and contribution of deep oxidation and increased
selectivity in 4-bromophthalonitrile up to 95.42–96.58%.
Keywords: ammonolysis, nitriles, kinetics, о-xylene
DOI : 10.1134/S107036321406005X
Previously [1–4] we studied the oxidative ammo-
nolysis of 4-bromo-о-xylene (I) and 4-bromo-о-tolu-
nitrile (II) on the oxide catalyst V–Sb–Bi–Zr/γ-Al2O3
and also considered the reaction mechanism which is
consistent with the observed kinetic regularities.
synthesized by potassium permanganate oxidation of
4-bromo-о-xylene to the corresponding acid followed
by dehydration of the latter into anhydride by
treatment with POCl3. The anhydride is used to prepare
first 4-bromophthalimide and then 4-bromophthalo-
nitrile in 30% yield. 4-Bromophthalonitrile was also
prepared by the ammonolysis of 4-bromophthalic
anhydride on an boron phosphate catalyst. In this case,
the yield of 4-bromophthalonitrile at 673 K was 50%.
Functionally substituted aromatic nitriles are ap-
plied in the synthesis of thermally stable polyimide
polymers, insecticides, liquid crystals, dyes, repellents,
and other valuable products [5]. 4-Bromophthalonitrile
is the starting material for the synthesis of 4,4'-(4,4'-
isopropylidenediphenoxy)bis(phthalic anhydride), a
monomer for polyetherimides which are processed by
modern technologies and use in electronics [6].
Targeted synthesis of phthalocyanines with desired
structure normally starts with functional derivatives of
corresponding phthalic acids, prefereably phthalo-
nitriles [2, 7, 8]. However, better soluble starting
materials are phthalocyanines containing alkylamino
or arylamino groups [9], which are prepared by the
copper-catalyzed reaction of halogenated phthalo-
cyanines with amines at elevated temperatures. One of
the possible synthetic approaches to amino-substituted
phthalonitriles involves nucleophilic substitution in
halophthalonitriles, including 4-bromophthalonitrile
[9]. In the latter work, 4- bromophthalonitrile was
4-Bromophthalonitrile can be synthesized in one
stage by vapor-phase oxidative ammonolysis which
combines oxidation and ammonolysis in one process
and is suitable both from the financial and engineering
viewpoints [7, 10, 11]. Shapovalov et al. [12] proposed
a procedure for synthesis of 4-bromophthalonitrile by
oxidative ammonolysis of 4-bromo-о-xylene [12] on
fused vanadium−titanium−tungsten oxide catalyst with
a 1 : 0.5 : 0.15 ratio at 643 K and the 4-bromo-о-
xylene–atmospheric oxygen–ammonia molar ratio
1 : 67 : 15. 4-Bromophthalonitrile was prepared in
yields of up to 62% at the process performance up to
86 g/L catalyst per hour.
In the present work we studied the synthesis of 4-
bromophthalonitrile by vapor-phase oxidative ammo-
nolysis of 4-bromo-о-xylene with high and medium
conversions in a one-stage and a recirculation pro-
cesses, respectively, and found an efficient catalysis
1
For communication IV, see [1].
1085

1086
BAGIRZADE, TAGIEV
Scheme 1.
O2, NH2
O2, NH2
CH3
CH3
CN
CN
CN
CH3
Br
Br
Br
Br
I
II
V
III
H2O
NH3
CO2
CN
CO
CO
NH
Br
IV
system for oxidative ammonolysis of 4-bromo-о-
xylene. It was established that the V–Sb–Bi/γ-Al2O3
catalyst modified with zirconium oxide is a good
contact catalyst for this reaction.
The study was performed in a gradientless reactor with
a vibratory fluidized bed by varying process param-
eters over a wide range [2–4].
Table 1 lists the experimental data obtained at
varied molar ratios of 4-bromo-о-xylene and oxygen in
the starting mixture. When the oxygen fraction in the
mixture is increased above some certain minimal value
[Р(O2)min], the conversion of the starting material and
the selectivity of its conversion into 4-bromo-
phthalonitrile sharply increase, and the quantity of the
4-bromo-о-tolunitrile intermediate therewith decreases.
Further variation of the molar ratio of the starting
compounds no longer affects the selectivity of the
process (Si) and the conversion of 4-bromo-о-xylene
(α). As seen from Table 1, as the temperature is
elevated to 693 K, 4-bromobenzonitrile starts to form.
Decrease of the oxygen fraction in the mixture below
[Р(O2)min] decreases the conversion, yields of 4-
bromophthalonitrile and СО2, and increases the yield
of the 4-bromo-о-tolunitrile intermediate. These
findings are likely to be explained by decreased degree
of oxygen contact with catalyst surface, which,
however, does not change the relative quantities of
specific oxygen species responsible for partial and
complete oxidation. Analogous reasoning can be found
in [18].
For the carrier we chose a microspherical alumina
which possesses a high mechanical strength. The
particle size of Al2O3 allows the process to be
performed in a fluidized catalyst bed. The carries was
subjected to special thermal pretreatment, and catalysts
samples were prepared by impregnating the carrier
with metal salts which enter in the composition of the
active mass [13].
The choice of catalyst and conditions for selective
conversion of 4-bromo-о-xylene into dinitrile is
complicated by the fact that ortho-substituents in
aromatic compounds hinder formation of nitriles but
facilitate formation of imides [7, 14, 15]. Therefore,
the major products of the oxidative ammonolysis of о-
xylene, as well as 4-bromo- and 4-phenyl-о-xylene are
the corresponding dinitriles and imides of о-phthalic
acid, which form a hardly separable crystal mixture
[16, 17].
It is important to note that the possibility of
intramolecular interaction at intermediate stages [11]
creates prerequisites for specific kinetic regularities
[2, 3], and this circumstance makes selectivity difficult
to control by varying process conditions.
The composition of the reaction products is much
affected by the fraction of ammonia in the starting
mixture. At a fairly low molar ratio of NH3 and 4-
bromo-о-xylene, the preferential reaction pathway is
deep oxidation of the starting compound, and the yield
of 4-bromophthalimide is fairly high even at quite a
short contact time (Table 2). As the NH3 : 4-bromo-о-
xylene molar ratio is increased, the yield of 4-
bromophthalonitrile increases but the conversion of 4-
bromo-о-xylene on the V–Sb–Bi–Zr/γ-Al2O3 oxide
catalyst is independent on the partial pressure of
According to the Scheme 1, 4-bromophtalonitrile
(III) is formed via 4-bromo-о-tolunitrile, and 4-bromo-
phthalimide (IV) is formed both by hydrolysis of 4-
bromophthalonitrile and directly from 4-bromo-о-
xylene; 4-bromobrnzonitrile (V) is formed from 4-bromo-
phthalimide and 4-bromo-о-tolunitrile (II).
To find optimal conditions for the recirculation
process, we first had to focus on the one-stage process.
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KINETICS OF OXIDATIVE AMMONOLYSIS OF 4-BROMO-о-XYLENE: V.
1087
Table 1. Effect of oxygen concentration of oxidative ammonolysis
of 4-bromo-о-xylenea
Table 2. Effect of ammonia concentration on oxidative ammo-
nolysis of 4-bromo-о-xylenea
I : NH3 : O2 : N2
molar ratio
Si, %
II
I : NH3 : O2 : N2
molar ratio
Si,%
IV
α, %
α, %
III
V
CO2
III
II
V
CO2
653 K
653 K
1 : 25 : 1.5 : 47.8
1 : 25 : 3.0 : 46.3
1 : 25 : 4.0 : 45.3
1 : 25 : 6.3 : 43.0
1 : 25 : 8.0 : 41.3
13.70 21.92 75.58
29.50 38.30 57.70
29.60 38.52 57.50
29.69 38.66 57.38
29.80 39.06 57.00
–
–
–
–
–
–
–
2.50
4.00
3.98
3.96
3.94
3.92
3.90
1 : 1.5 : 6.3 : 66.5 29.50 25.57 48.79 9.78
1 : 3.0 : 6.3 : 65.0 29.40 32.37 52.35 5.34
1 : 7.0 : 6.3 : 61.0 29.60 37.59 53.65 2.43
1 : 12.0 : 6.3 : 56.0 29.75 37.90 55.46 1.38
–
–
–
–
–
–
–
–
15.86
9.94
6.33
5.26
3.90
3.96
3.94
3.92
1 : 15.0 : 6.3 : 53.0 30.00 39.48 56.62
1 : 25.0 : 6.3 : 43.0 29.69 38.66 57.38
1 : 35.0 : 6.3 : 33.0 29.80 39.06 57.00
1 : 45.0 : 6.3 : 23.0 29.90 39.28 56.80
693 K
–
–
–
–
1 : 25 : 12.0 : 37.3 29.90 39.28 56.80
1 : 25 : 15.0 : 34.3 30.00 39.48 56.62
693 K
1 : 25 : 2.0 : 47.3
1 : 25 : 4.0 : 45.3
1 : 25 : 6.3 : 43.0
1 : 25 : 8.0 : 41.3
27.00 49.30 45.90
–
4.80
62.20 58.19 31.70 1.69 8.42
62.30 58.53 31.40 1.67 8.40
62.40 58.29 31.65 1.68 8.38
1 : 1.5 : 6.3 : 66.5 61.90 28.35 24.00 16.16 1.49 30.00
1 : 3.0 : 6.3 : 65.0 62.00 39.46 28.20 8.74 1.60 22.00
1 : 7.0 : 6.3 : 61.0 62.10 50.22 30.10 3.69 1.64 14.35
1 : 12.0 : 6.3 : 56.0 62.40 54.16 30.61 2.00 1.65 11.58
1 : 25 : 12.0 : 37.3 62.50 58.13 31.82 1.69 8.36
1 : 25 : 15.0 : 34.3 62.60 57.96 32.00 1.70 8.34
a Contact time 0.27 s.
1 : 15.0 : 6.3 : 53.0 62.60 57.96 32.00
1 : 25.0 : 6.3 : 43.0 62.30 58.53 31.40
1 : 35.0 : 6.3 : 33.0 62.20 58.19 31.70
1 : 45.0 : 6.3 : 23.0 62.50 58.13 31.82
a Contact time 0.27 s.
–
–
–
–
1.70 8.34
1.67 8.40
1.69 8.42
1.69 8.36
ammonia in the reaction mixture. In the presence of
large quantities of ammonia, the yield of 4-
bromobenzonitrile changes only slightly, whereas at
minimal concentrations of ammonia, i.e. at [P(NH3)] >
[P(NH3)min], a zero reaction order in ammonia is
realized. Deacrese off the fraction of ammonia in the
reaction mixture to [P(NH3)] < [P(NH3)min] results in
intensification of deep oxidation of 4-bromo-о-xylene
to СО2 and 4-bromophthalimide. Probably, ammonia
functions here not only as a reagent, but also as a
modifier of catalyst surface and blocks deep oxidation
centers of 4-bromo-о-xylene and affects the nature of
catalytic centers, thus favoring more selective
formation of 4-bromophthalonitrile.
formation of 4-bromophthalimide and 4-benzene is
observed, and their yield increases with contact time.
Figure 2 shows the temperature dependences of
treaction selectivity. As the temperature is elevated to
693 K, the selectivity of 4-bromo-о-xylene conversion
into 4- bromophthalonitrile increases, and the yields of
4-bromo-о-tolunitrile and 4-bromophthalimide decrease.
High temperatures favor more rapid formation of 4-
bromobenzonitrile and СО2: Their show increased
yields at high temperatures.
The resulting kinetic regularities allowed us to
determine optimal conditions for the one-stage process:
673 K, τ 1.55–1.60 s, I : NH3 : air molar ratio 1 : 15 : 30.
Figure 1 shows the dependences of the conversion
of 4-bromo-о-xylene and reaction selectivity on
contact time (τ). As τ increases, the yield of 4-bromo-
phthalonitrile increases, and the yield of 4-bromo-о-
tolunitrile decreases. However, at high τ values,
The optimal conditions were chosen on a laboratory
installation with a fluidized-bed reactor 40 mm in
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1088
BAGIRZADE, TAGIEV
Contact time, s
T, K
Fig. 1. Dependence of the results of oxidative ammonolysis
of 4-bromo-о-xylene (I) on contact time at 673 K and I :
NH2 : O2 molar ratio 1:15:6.3. (1) Conversion of compound
I (α) and (2–6) selectivity of formation (Si) of compounds
III, II, CO2, V, and IV, respectively.
Fig. 2. Dependence of the results of oxidative ammonolysis
of 4-bromo-о-xylene (I) on temperature at the contact time
1.23 s and I : NH2 : O2 molar ratio 1:15:6.3. (1) Conversion
of compound I (α) and (2–6) selectivity of formation (Si) of
compounds III, II, IV, CO2, and V, respectively.
diameter. The parameters of the process and its results
are listed below.
preparing phthalocyanine dyes are quite severe [16],
we considered it more reasonable to turn to the process
scheme which provides a medium conversion of 4-
bromo-о-xylene with recirculation.
Temperature, K
663–673
1.55
Contact time, s
Analysis of the kinetic data (Table 2) shows that 4-
bromophthalimide (IV) is formed at high ammonia
concentrations (beginning with 15 mol NH3/mole
substrate) by hydrolysis of 4-bromophthalonitrile with
water (see scheme) which results from side reactions
[16, 19], specifically, oxidative dehydrogenation and
deep oxidation of 4-bromo-о-xylene. In the medium
conversion range of 4-bromo-о-xylene, at a short
contact time the target dinitrile does not have enough
time to undergo the secondary conversion into imide.
I : NH3 : air molar ratio
Conversion of compound I, %
Selectivity of formation, % :
III
II
IV
V
CO2
1 : 15 : 30
93.70
79.85
7.50
2.85
3.96
5.84
As seen from these data, the yield of 4-
bromophthalonitrile on the V–Sb–Bi–Zr/γ-Al2O3 oxide
catalyst is 74.82 mol % per 4-bromo-о-xylene. Taking
into account that 4-bromophthalonitrile is quite
difficult to purify from 4-bromo-о-tolunitrile, 4-bromo-
benzonitrile, and 4-bromophthalimide, especially from
4-bromophthalimide crystals, while the requirements
to 4-bromophthalonitrile as the starting material for
Table 3 lists the results of oxidative ammonolysis
of mixtures of 4-bromo-о-xylene and 4-bromo-о-
tolunitrile. As seen, an almost quantitative yield of 4-
bromophthalonitrile per reacted 4-bromo-о-xylene can
be provided.
Unlike what is observed with the one-stage process,
when the process on the V–Sb–Bi–Zr/γ-Al2O3 oxide
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KINETICS OF OXIDATIVE AMMONOLYSIS OF 4-BROMO-о-XYLENE: V.
1089
Table 3. Oxidative ammonolysis of mixtures of 4-bromo-о-xylene and 4-bromo-о-tolunitrileа
Yield,c mol %
Т, K
Compounds in the system
Fed to the reactor, mmol/h Obtained, mmol/h α,b %
III
CO2
2.7
633
14.05
4.69
11.46
4.69
2.52
0.07
9.91
4.75
3.91
0.17
7.54
4.81
6.01
0.38
18.4
29.5
46.3
97.3
I
II
III
CO2
I
653
673
14.05
4.69
94.4
92.3
4.0
5.8
II
III
CO2
I
14.05
4.69
II
III
CO2
a Contact time 0.27 s, (I + II) : O2 : NH3 molar ratio 1 : 6.3 : 15. b Coversion of compound I. c Per reacted 4-bromo-о-xylene (I).
catalyst is performed at a short contact time at 638–
653 K and the I : air : NH3 molar ratio of 1 : 30 : 15
with 50–60% conversion and recirculation of
unreacted 4-bromo-о-xylene and intermediate 4-
bromo-о-toludinitrile, the selectivity in 4-bromo-
phthalonitrile results increases to 95.42–96.58%, and
the yield of by-products (4-bromophthalimide and 4-
bromobenzonitrile) and the contribution of the deep
oxidation to СО2 decrease. Therewith, the recirculation
product is ~1.7–2.0. Consequently, the process with
recirculation excludes the stage of purification of the
target product and is continuous, highly selective, and
efficient. Taking into account that decrease of the
conversion depth in the one-stage process decreases
the reaction volume and, consequently, reactor
efficiency [20], increase of selectivity in 4-bromo-
transformations of the substrate.
In the case of recirculation, 4-bromophthalonitrile
and СО2 are the only reaction products. The contact
gases contain O2, NH3, N2, CO2, HBr, 4-bromo-о-
xylene, 4-bromo-о-tolunitrile, and 4-bromophthalo-
nitrile. The unreacted 4-bromo-о-xylene and inter-
mediate 4-bromo-о-tolunitrile, separated from 4-
bromophthalonitrile, are returned into the reactor.
Therefore, the engineering design of the process
should envision separation and entrapping of solid and
liquid reaction products contained in contact gases,
isolation of 4-bromophthalonitrile from the product
mixture, return of unreacted 4-bromo-о-xylene and 4-
bromo-о-tolunitrile into the reactor, and regeneration
of excess ammonia and its recirculation.
The quality characteristics of 4-bromophthalonitrile
prepared by recirculation of 4-bromo-о-xylene are
listed below:
phthalonitrile on recirculation ensures
a
high-
efficiency process. The catalyst efficiency on recir-
culation is ~3 times higher than in the one-stage
process, which at a high conversion of 4-bromo-о-
xylene makes ~175 g/L catalyst per hour [19].
Moreover, because of the higher conversion of 4-
bromo-о-xylene in the one-stage process, the yield of
СО2, a product of the highly exothermal complete
oxidation reaction, increases, which, in its turn,
prevents efficient heat abstraction and reactor control
[19, 21]. Since the selectivity problem is one of the
central problems in the theory of catalysis [22], of
primary importance is the selectivity of the catalyst,
i.e. efficient contact preferably drives only one of the
multitude of thermodynamically possible oxidative
Main substance content, wt %
Melting point, K
Calcination residue, wt %
Moisture content, wt %
99.62–99.80
393.0–393.5
0.03–0.05
0.17–0.33
No 4-bromophthalimide admixture was detected
Thus, the proposed procedure (recirculation) makes
it possible to develop an efficient one-stage technology
for the production of 4-bromophthalonitrile by
oxidative ammonolysis of 4-bromo-о-xylene.
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BAGIRZADE, TAGIEV
USSR Inventor’s Certificate no. 1057491, 1982, Byull.
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