Ion-exchange resin catalysts in the liquid-phase hydrazinolysis of cinnamic acid

Article abstract of DOI:10.1134/S0023158417010025

The catalytic activity of a synthetic ion-exchange resins has been studied in the reaction of cinnamic acid with hydrazine (aqueous medium, 363 K, 1.0–2.5 h) yielding the corresponding hydrazide. Efficient catalysts for the process are the anion-exchange resins AV-17-8 and AN-31. The modifying effect of the substrate—hydrazine hydrate—on the catalytic properties of the ion-exchange systems has been demonstrated. On the basis of IR spectroscopic studies, a plausible process mechanism was suggested. It involves polymer-bound quaternary ammonium ions of the anion exchanger.

Full text of DOI:10.1134/S0023158417010025

ISSN 0023-1584, Kinetics and Catalysis, 2017, Vol. 58, No. 1, pp. 24–27. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © S.A. Dzhumadullaeva, A.B. Baeshov, 2017, published in Kinetika i Kataliz, 2017, Vol. 58, No. 1, pp. 26–29.
Ion-Exchange Resin Catalysts in the Liquid-Phase Hydrazinolysis
of Cinnamic Acid
S. A. Dzhumadullaeva* and A. B. Baeshov
Kh. A. Yassawi International Kazakh–Turkish University, Turkestan, 161200 Kazakhstan
*e-mail: sveta.jumadullayeva@ayu.edu.kz
Received February 17, 2016
Abstracts—The catalytic activity of a synthetic ion-exchange resins has been studied in the reaction of cin-
namic acid with hydrazine (aqueous medium, 363 K, 1.0–2.5 h) yielding the corresponding hydrazide. Effi-
cient catalysts for the process are the anion-exchange resins AV-17-8 and AN-31. The modifying effect of the
substrate—hydrazine hydrate—on the catalytic properties of the ion-exchange systems has been demon-
strated. On the basis of IR spectroscopic studies, a plausible process mechanism was suggested. It involves
polymer-bound quaternary ammonium ions of the anion exchanger.
Keywords: ion-exchange resin catalysts, liquid-phase hydrazinolysis, cinnamic acid
DOI: 10.1134/S0023158417010025
Interest in synthetic derivatives of cinnamic acid is centration, and enable one to avoid high water
caused by the possibility of synthesizing, on their consumption and equipment corrosion.
basis, antituberculosis and hepatoprotective drugs and
antioxidants. [1]. For example, cinnamic acid hydra-
zide is active against Mycobacterium tuberculosis. It
provides a basis for the synthesis of a number of other
physiologically active substances [2]. For this reason,
methods for the synthesis of cinnamic acid derivatives
have been extensively studied, particularly the hydraz-
inolysis reaction of carboxylic acids and their esters.
Cinnamic acid hydrazide was synthesized [3] by cin-
namic acid esterification followed by the hydrazinoly-
sis of the ester in absolute ethanol. However, disad-
vantages of this method are the low yield of cinnamic
acid hydrazide (55%) and the necessity of employing
solvents that can impair the organoleptic properties of
the product. Because of the latter circumstance, the
product needs to be additionally purified.
The aim of this work was to study the catalytic
activity of a number of synthetic ion-exchange resins
in the reaction between cinnamic acid and aqueous
hydrazine and to optimize the reaction conditions.
EXPERIMENTAL
The following commercial synthetic ion exchange
resins were used as catalysts: highly basic anion
exchanger AV-17-8 (grain size 0.4–0.6 mm), weakly
basic anion exchangers AN-31 (0.4–2.0 mm) and
AN-1 (0.45–0.50 mm), strongly acidic sulfonic acid
cation-exchange resin KU-2-8 (0.40–0.55 mm), and
phosphoric acid cation exchanger KRF-10P (0.5–
1.0 mm). They were conditioned and converted into
Н+/ОН–-form by a standard method [6]. The
exchange capacity of the ion exchangers was measured
under static conditions by a standard method [7].
Cinnamic acid hydrazide was synthesized from
cinnamic acid by reacting it with hydrazine hydrate in
the presence of an ion-exchange resin catalyst. Exper-
iments were carried out in a static system in a tempera-
ture-controlled 250-cm3 glass reactor equipped with a
mechanical stirrer, thermometer, and reflux con-
denser using commercial hydrazine hydrate (99.9%)
The hydrazinolysis of carboxylic acids in an aque-
ous medium by the action of a basic catalyst is more
promising, for it allows obtaining hydrazides of aro-
matic and heterocyclic carboxylic acids in a single
step. We have demonstrated the possibility of using ion
exchange resins and synthetic zeolites as catalysts for
hydrazinolysis of 4-cyanopyridine and benzoic acid in
the synthesis of the corresponding hydrazides [4, 5].
Ion-exchange resin catalysts based on styrene– and cinnamic acid (reagent grade). The reaction mix-
divinylbenzene copolymers have several advantages: ture, which consisted of cinnamic acid, hydrazine
they are very selective, allow the reaction to be con- hydrate, water and an air-dry ion exchanger, was
ducted under relatively mild conditions, are easily sep- heated in a water bath at 363 K for 1–2.5 h. Next, the
arable from the reaction mixture (which allows a con- mixture was cooled and the ion exchanger was filtered
tinuous process,) do not require neutralization or con- out. The aqueous phase was evaporated to dryness at
24

ION-EXCHANGE RESIN CATALYSTS IN THE LIQUID-PHASE HYDRAZINOLYSIS
25
Table 1. Cinnamic acid hydrazinolysis over the ion-exchange resin catalysts*
Exchange capacity of the ion
exchanger, mg-equiv/g
CAH yield,
Catalyst
CA conversion, %
%
AV-17-8
AN-31
AN-1
KU-2-8
KRF-10P
4.2
3.8
3.6
3.0
3.2
94
92
87
80
82
90
78
74
62
69
* Reaction conditions: CA : HH : Cat : Н О = 1 : 0.72 : 2 : 16, 363 К, 2 h.
2
Table 2. CAH synthesis over the anion exchanger АV-17-8(ОН–) (363 К)
CA : HH : Cat : Н2О
CA : HH : Cat : Н2О
Time, h
CAH yield, %
Time, h
CAH yield, %
1 : 0.72 : 2 : 16
1 : 0.72 : 2: 16
1 : 0.72 : 2 : 16
1 : 0.72 : 2 : 16
1 : 0.72 : 0.5 : 16
1 : 0.72 : 1.0 : 16
1 : 0.72 : 1.5 : 16
1.0
1.5
2.5
2.0
2.0
2.0
2.0
56
63
87
90
68
82
85
1 : 0.60 : 2 : 16
1 : 0.80 : 2 : 16
1 : 1.10 : 2 : 16
1 : 0.72 : 2 : 8
1 : 0.72 : 2 : 10
1 : 0.72 : 2 : 12
1 : 0.72 : 2 : 20
2.0
2.0
2.0
2.0
2.0
2.0
2.0
76
87
78
64
69
81
89
333 K. The dry residue was recrystallized from abso-
lute ethanol. The resulting hydrazide had a melting
point of 373–374 K. Its composition was determined
by elemental analysis. For C9H10N2O calcd., %: C,
The introduction of hydrazine hydrate, a strong
base, to the reaction mixture smoothes the catalytic
action of ion exchangers with different acid–base
properties. According to the literature [9], in acid–
66.59; H, 6.16; N, 17.26. Found, %: С, 66.35; Н, 6.27; base catalysis the reaction medium can change the
N, 17.39. IR spectrum, ν, cm–1: 1693 (C=O), 1541
(CH=CH), 3210, 3340 (N–H), 3027 (C–H)Ar, 1182
(C–N), and 989 (N–N).
degree of hydration and the strength of acid sites and
the proportions of Lewis and Brønsted sites, thus
altering the character of the processes. In our case, the
modifying effect of the substrate (hydrazine hydrate)
shows itself most clearly: the acidic ion exchangers
KU-2-8 and CRF-10P acquire the ability to accelerate
the reaction, which typically occurs in the presence of
a basic catalyst.
The reaction was monitored using photocolorimet-
ric analysis [8]. The IR spectra of the starting materials
and the reaction product (in KBr pellets) were
recorded on an Impact-410 spectrometer (Melles
Griot, United States) in the 400–4000 cm–1 range.
In addition to being composition- and structure-
dependent, the activity and selectivity of the ion
exchangers are strongly influenced by the operating
conditions. For AV-17-8 in ОН– form, depending on
the contact time, on the proportions of the reactants,
and on the amount of catalyst, the CAH yield ranges
from 56 to 90% of the theoretical yield (Table 2). It was
found that the optimal conditions for the synthesis of
the hydrazide at 363 K are the following: duration, 2 h;
CA : HH : Cat : H2O weight ratios of 1 : 0.72 : 2 : 16.
RESULTS AND DISCUSSION
Under the conditions examined, the main product
of the reaction between cinnamic acid (CA) and hydra-
zine hydrate (HH) is cinnamic acid hydrazide (CAH).
C6H5CH=CHCOOH + NH2−NH2
Cat
C6H5CH=CHCONHNH2 + Η2Ο.
The literature [10] suggests that the cinnamic acid
hydrazinolysis reaction in the presence of ion
exchange resin AV-17-8 (OH-) proceeds via a hetero-
geneous catalytic mechanism in which the polymer-
bound quaternary ammonium ions and hydroxyl ions
are responsible for the process:
As can be seen from Table 1, all tested catalysts are
active in this process: the conversion of CA is 80–94%,
and the CAH yield is 62–90%. The highest CAH yield
(78–90%) with a CA-to-hydrazide conversion selectiv-
ity of 84–95% is obtained with AV-17-8 and AN-31
(Table 1). AN-1 is slightly inferior to them. On passing
from the highly basic anion exchanger AV-17-8 to the
acidic cation exchangers KU-2-8 and KRF-10P, the
catalytic activity and selectivity decrease considerably.
(CH3)3N+OH−
~
(CH3)3N++ OH−.
~
KINETICS AND CATALYSIS Vol. 58 No. 1 2017

26
DZHUMADULLAEVA, BAESHOV
The adsorption of cinnamic acid on the anion- anions, which block the fixed groups of the resin
exchange resin results in the formation of carboxylate according to the following scheme:
O
C6H5 CH CH
C
N+(CH3)3OH−
~
+
nH2O
·
OH
−
O
N+(CH3)3
~
(n + 1)H2O.
C6H5−CH=CH−C
·
O
In the spectrum characterizing the interactions of
cinnamic acid with AV-17-8 (OH), there is no very
intense absorption bands at ~ 1643 cm–1 that is due to
The IR spectrum of the anion exchanger that
is in contact with hydrazine hydrate practically
does not differ from the spectrum of the initial
the stretching vibrations of the C=O group of cin- anion exchanger, indicating that there is no
namic acid. Against the background of the own bands
of the anion exchanger (figure), intense absorption
bands at 1396 and 1689 cm–1 appear, which can be
assigned to symmetric and antisymmetric vibrations of
the carboxylate group –COO– [11].
adsorption of hydrazine. Consequently, the car-
boxylate anion‒catalyst complex decomposes
under the action of hydrazine from the reaction
medium bulk to yield the desired hydrazide, regen-
erating the active site.
−
O
N+(CH3)3
(n + 1)H2O
C6H5−CH=CH−C
·
O
~
O
NH2−NH2 · H2O
+ N+(CH ) OH−
C6H5 −CH=CH−C
nH2O.
·
3 3
NHNH2
~
A similar mechanism was proposed in the case of hydrazinolysis of cinnamic acid over a catalyst with
basic sites (anion-exchange resin), a similar reaction
mechanism can be expected.
catalysis of benzoic acid hydrazinolysis by AV-17-8 in
ОН– form [5]. Consequently, for the liquid-phase
CONCLUSIONS
1541
1643
1380
The most effective catalysts for the selective hydra-
zinolysis of cinnamic acid are the ion exchange resins
with basic properties, namely, АВ-17-8 and AN-31.
Over these catalysts, the cinnamic acid conversion is
92–94% and the CAH yield is 78–90%. The modify-
ing effect of hydrazine hydrate was demonstrated in
the case of the acidic catalysts KU-2-8 and KRF-10P.
The catalytic cinnamic acid hydrazide synthesis con-
ditions ensuring 56–90% hydrazide yield for the anion
exchanger AV-17-8(OH–) in an aqueous medium were
found. A plausible hydrazinolysis mechanism over the
anion exchanger was suggested on the basis of IR spec-
troscopic studies. This mechanism involves polymer-
bound quaternary ammonium ions.
1
1600
1689
1396
2
1000
2000
3000
4000
Wavenumber, cm–1
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