Novel aqueous soluble cobalt(II) phthalocyanines of tetracarboxyl-substituted: Synthesis and catalytic activity on oxidation of sodium diethyldithiocarbamate

Article abstract of DOI:10.1142/S1088424614501028

Enhancement of the catalytic activity of phthalocyanine catalysts by immobilizing them on polymer matrix has been studied. It has been found that the immobilization of cobalt(II) phthalocyanines on polymers enhances their catalytic activity in the oxidation of sodium diethyldithiocarbamate by air oxygen under mild conditions.

Full text of DOI:10.1142/S1088424614501028

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2014; 18: 1–9
DOI: 10.1142/S1088424614501028
Published at http://www.worldscinet.com/jpp/
Novel aqueous soluble cobalt(II) phthalocyanines
of tetracarboxyl-substituted: Synthesis and catalytic activity
on oxidation of sodium diethyldithiocarbamate
Artur Vashurin*a◊, Vladimir Maizlishb, Svetlana Pukhovskayaa, Alena Voroninaa◊◊,
Ilya Kuzmina◊◊, Natalya Futermana, Oleg Golubchikovc and Oskar Koifmand
a Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology, Ivanovo 153000, Russia
b Department of Technology of Fine Organic Synthesis, Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
c Department of Organic Chemistry, Ivanovo State University of Chemistry and Technology, Ivanovo 153000, Russia
d Department of Chemistry and Technology of Macromolecular Compounds, Ivanovo State University of Chemistry
and Technology, Ivanovo 153000, Russia
Received 5 September 2014
Accepted 7 October 2014
ABSTRACT: Enhancement of the catalytic activity of phthalocyanine catalysts by immobilizing them on
polymer matrix has been studied. It has been found that the immobilization of cobalt(II) phthalocyanines
on polymers enhances their catalytic activity in the oxidation of sodium diethyldithiocarbamate by air
oxygen under mild conditions.
KEYWORDS: phthalocyanine, synthesis, homogeneous catalysis, immobilization, heterogeneous
catalysis.
distributions, catalyst stability and the rate of the
INTRODUCTION
oxidation processes [12–18].
Metallophthalocyanines (MPc) have been extensively
One of the most important applications of MPc’s
studied due to their unique optical, electronic, catalytic
has been in catalysis, including large-scale industrial
and photocatalytic properties. Phthalocyanine complexes
processes. For instance, the Merox process, referred to as
of transition metals are attractive as potential oxidation
“sweetening” in the petroleum refining industry, involves
catalystsbecauseoftheirrathercheapandfacilepreparation
catalytic oxidation of mercaptans in the presence of
in a large scale and their chemical and thermal stability.
sulfonated cobalt phthalocyanines to remove a major part
The substitution at the peripheral positions of the
of sulfur from petrol [19, 20].
macrocycle can alter the physico-chemical properties
Catalytic action of CoPc’s may be explained by
of the phthalocyanines [1–5]. Attaching of anionic
coordination as well as associative mechanisms. In
groups such as sulfonic or carboxylic to MPcs render
the former case oxidation occurs thanks to coordi-
them water-soluble. Additionally by altering the nature
nation of the oxygen molecule by the central metallo-
of the substituents, one can control phthalocyanine
phthalocyanine cation from one side and anion from the
solubility in various solvents [6–11]. Therefore, there
other side of the macrocycle plane, and the transfer of
has been much research on catalyst modifications in
order to optimize the selectivity, product yields and
electron from oxygen to the substrate via cobalt cation
[12, 21–27].
This mechanism can be represented by the following
scheme:
◊ SPP full and ◊◊ student member in good standing
*Correspondence to: Artur Vashurin, email: asvashurin@mail.
ru, tel: +7 (910)-990-9125
i
Co(II)Pc + RS-
Co(I)Pc⋅RS
(1)
ꢀꢀꢁ
ꢂꢀꢀ
Copyright © 2014 World Scientific Publishing Company

2
A. VASHURIN ET AL.
-
2
-
Co(I)Pc⋅RS- + O
O ⋅ Co(II)Pc⋅RS
RESULTS AND DISCUSSION
ꢀꢀꢁ
2 ꢂꢀꢀ
(2)
(3)
(4)
(5)
O-2 ⋅Co(II)Pc⋅RSi
Co(III)Pc⋅O + RS
-
2
i
ꢀꢀꢁ
ꢂꢀꢀ
The state in solutions
2RSi → RS- RS
Data about aggregation of carboxyl derivatives
of metallophthalocyanines in aqueous solutions are
available in the literature. Thus, authors of [43–46]
determined thermodynamic parameters for dimerization
of cobalt complexes of 3-carboxyl and 4-carboxyl
substituted phthalocyanines in which carboxyl group is
directly bound to the macrocycle. It is also assumed that
association occurs due to the formation of p–p dimers
and m-oxo-dimers.
Introduction of the spacer chain with a heteroatom
between the functional group and the macrocycle leads
to the change in associate state of cobalt phthalocyanine.
Studies on the monomer-dimer equilibrium of
CoPc(NH–C6H4–COOH)4 and CoPc(S–C6H4–COOH)4
were performed in the water-alkaline solution with pH 8,
because it has been found out earlier, that water-alkaline
solutions with pH within 7.6–8.2 range are optimal for
the catalysis [47].
Co(III)Pc⋅O-
Co(II)Pc + O
ꢀꢀꢁ
2 ꢂꢀꢀ
2
However, CoPc as a homogeneous catalyst in aqueous
and non-aqueous solution is usually prone to aggregate
at a relatively low concentration, negatively resulting in
catalytically inactive dimers [28, 29]. One can control an
associate state of phthalocyanines by altering the nature
of periphery substituents, as well as by introducing
coordinating additives into the solution [14–22, 28, 29].
Homogeneous catalysts have proven ineffective in
the manufacturing as their separation from the reaction
products involves certain difficulties. This disadvantage
can be eliminated by using phthalocyanines on various
carriers, such as activated coal, coal-graphite cloth, [30–
32] silicon dioxide [23, 33–38], organic polymers [39],
cotton fabric [40], ceolites [41], etc. At the same time,
catalytic activity of heterogeneous catalysts is lower than
homogeneous ones [34–36].
It has been found out in this work that associated
forms of cobalt complexes have much higher activity
as compared with non-associated ones, and that
immobilizing catalyst on the surface of polyester fabric
increases its activity.
In our previous works [36, 39, 42], it was demonstrated
that tetrasulfo-derivatives of cobalt(II)phthalocyanine
that underwent immobilization on the surface of silicon
dioxide and organic polymers are effective catalysts for
oxidation of sodium diethyldithiocarbamate in water-
alkaline solutions. This oxidation process repeatedly
gave stable results.
Investigation of the dependence between UV-vis spectra
and CoPc(NH–C6H4–COOH)4 concentration (Fig. 1)
demonstrates that metallophthalocyanine is present mainly
in the form of a monomer.
One observes adsorption maximum of 730 nm
(Q-band) with a slight slope at 650 nm, which was
reported in [48–50] and is known to be unique for non-
associated macrocycle forms.
The changes in UV-vis spectra within 10-4–10-6
M
concentration range for Q-band obey a Beer–Lambert
law, which indicates that a single chromophore species
is present in the system, namely the monomers of
CoPc(NH–C6H4–COOH)4 with the molar coefficient of
extinction (e) as high as 11440 50 l/(mol×ꢀcm).
In this study, phthalonitriles and based on them
phthalocyanineshavebeensynthesized.Thesecompounds
contain carboxyl substituents attached to the macrocycle’s
periphery through a spacer group. Phthalocyanines
are immobilized on the surface of a polymeric matrix.
Catalytic activity of metallophthalocyanines in both
homogeneous and heterogeneous oxidation of sodium
diethyldithiocarbamate has been investigated. Choice as
a model reaction of oxidation of sodium diethyldithio-
carbamate caused by a number of factors, such as a low
toxicity of the compound, a sufficient amount of data
on the kinetics and mechanism of oxidation of sodium
diethyldithiocarbamate, the solubility of the compound
in water, the ability to control the concentration of
sodium diethyldithiocarbamate in any given reaction
time, etc. Also important is that in the oxidation of
sodium diethyldithiocarbamate formed tetraethylthiuram
disulfide, a high degree of purity. The tetraethylthiuram is
commonly used to treat chronic alcoholism by producing
an acute sensitivity to alcohol.
Fig. 1. UV-vis spectra of CoPc(NH–C6H4–COOH)4 in water-
alkaline solution (pH 8) c = 2 × 10-5 M at 298.15 K
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 2–9

NOVEL AQUEOUS SOLUBLE COBALT(II) PHTHALOCYANINES OF TETRACARBOXYL-SUBSTITUTED
3
Fig. 2. Optical density (l 630 nm) of water-alkaline solution
(pH 8) of CoPc(S–C6H4–COOH)4 against concentration of the
macrocycle at 298.15 K
Fig. 3. UV-vis spectra of CoPc(S–C6H4–COOH)4 in water-
alkaline solution with pH 8: (1) dimeric form (without Py);
(2) monomer-dimer equilibrium; (3) monomeric form mainly
(with excess of Py)
During titration of water-alkaline solution of
CoPc(NH–C6H4–COOH)4 with pyridine, one observes
the decrease in the intensity of an adsorption Q-band and
its bathochromic shift by 30 nm which is characteristic
for axial coordination. Isosbestic points are observed
during titration. The resulting complex of CoPc(NH–
C6H4–COOH)4 with pyridine is stable (Ky = 3200 300
l/mol). Replacing nitrogen heteroatom with sulfur in a
spacer chain results in drastic changes in macrocycle
associate state.
Recorded UV-vis spectra of CoPc(S–C6H4–COOH)4
are typical for associated forms of metallophthalocyanine
(Fig. 2). When studying concentration dependence in the
range from 3 × 10-3 up to 3 × 10-5 M of CoPc(S–C6H4–
COOH)4 in water-alkaline solution (pH 8), we observed
gradual decrease of intensity of 635 nm adsorption band.
The band remains broadened, which is characteristic for
an associate form of phthalocyanine.
Based on the structure of metallophthalocyanine mole-
cules and spectral data, we can assume that CoPc(S–
C6H4–COOH)4 forms p–p dimers. Dissociation constants
of dimers (K1) were calculated according to the procedure
recommended in [51, 52]. It should be noted that dimers
of CoPc(S–C6H4–COOH)4 are quite labile (K1 = 8.4 ×
10-4 1 × 10-5 M) and addition of polar solvents which
are able to axially coordinate to the central metal cation
can be used to control self-association of CoPc(S–C6H4–
COOH)4 in water-alkaline solutions.
Stability constant of the molecular complex of
CoPc(S–C6H4–COOH)4 with pyridine (K2 = 3200 300 l/
mol) was equal to the constant of similar complex of
CoPc(NH–C6H4–COOH)4, which indicates that both
compounds have identical state of the reaction center
during molecular complexation.
A Beer-Lambert law is obeyed only at rather high
concentrations >10-4 M, which can be explained by
the equilibrium completely shifted toward dimer form
(Fig. 2),
Homogeneous catalysis
K1
If concentration of oxygen, catalyst and pH of the
solution remain constant, the rate of DTC oxidation
reaction is described by the first-order kinetic equation:
(6)
ꢀꢀꢀꢁ
(MPc)
MPc + MPc
2 ꢂ ꢀ ꢀꢀ
Adding pyridine (Fig. 3), as an axial ligand to water-
alkaline solution of CoPc(S–C6H4–COOH)4 leads to the
formation of molecular complexes, causing association
equilibrium to shift toward monomeric forms of the
macrocycle.
dc
= -keff ⋅c
(8)
dt
where c — is DTC concentration, t — is time, keff is the
reaction rate constant, s-1.
The order of reaction with respect to DTC is confirmed
by the linear type of dependence when lnc = f(t) is plotted
(Fig. 4), as well as by the same values of reaction rate
constants calculated using the following equation:
K2
ꢀꢀꢀꢁ
(7)
(MPc) + 2Py
2MPc⋅Py
ꢂ ꢀ ꢀꢀ
2
The curve of spectrophotometric titration is complex
which indicates that both dimer dissociation and the
formation of molecular complexes with pyridine are
taking place in the system.
keff = (l/ t)⋅ln(c c)
(9)
/
0
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 3–9

4
A. VASHURIN ET AL.
Fig. 4. Kinetic curves of DTC oxidation at 298.15 K in the
presence of (1) CoPc(S–C6H4–COOH)4 (c = 6.52 × 10-5 M);
(2) CoPc(NH–C6H4–COOH)4 (c = 3 × 10-5 M)
Fig. 5. UV-vis spectra of CoPc(S–C6H4–COOH)4 in quinoline
solution: (1) to immobilize (c = 3 × 10-4 M); (2) immobilized
on Lavsan
where c0 is the initial DTC concentration, c is DTC
concentration at a given moment of time (t).
DTC is hardly oxidized by ambient oxygen without
the catalyst (keff =ꢀ1.7 × 10-5 s-1), which suggests that it is
the catalyst introduced into the system that is responsible
for the results described above.
CoPc(NH–C6H4–COOH)4 which in water solutions
is predominantly in monomeric form did not show
high catalytic activity. E.g. when concentration of
the macrocycle in the reaction mixture is 3 × 10-5 M,
reaction rate constant is keff = 25 × 10-5 s-¹ which confirms
the idea discussed in the literature that association
reduces catalytic activity and the macrocycle in a stable
monomeric form is unfavorable for the catalysis.
structures. It should be noted that the effective oxidation
of DTC will proceed in alkaline medium only, where
thiol is present in the form of RS anion. DTC oxidation in
the presence of homogeneous catalysts obeys the kinetic
first-order equation. This fact concluding that the limiting
stage of the process is the formation of RS radical, which
in turn forms the RS-SR chain.
The incorporation of oxygen and the molecule
undergoing oxidation into associate cavity stimulates
their interaction. High catalytic activity is probably due
to a hybrid mechanism of action of a catalyst including
both associate and coordination component.
CoPc(S–C6H4–COOH)4 showed
a
much better
Heterogeneous catalysis
result. When it is present in 3 × 10-5 M concentration,
reaction rate constant is keff = 51 × 10-5 s-¹, in spite of
the fact that in contrast to CoPc(NH–C6H4–COOH)4 in
studied concentration range this macrocycle forms dimer
To increase catalytic activity and eliminate
aggregation, CoPc(S–C6H4–COOH)4 was immobilized
into a polymeric matrix of Lavsan. Pre-treatment of the
Table 1. Effective rate constants of DTC oxidation in the presence of the catalyst: CoPc(S–C6H4–COOH)4–Lavsan at 298.15 K and
pH 8.4
The time of Lavsan
treatment by
Microwave
Concentration of
Time of treatment of activated
keff × 105, s-1
cRSSR, %
radiation power, W CoPc(S–C6H4–COOH)4 Lavsan by CoPc(S–C6H4–COOH)4,
microwaves, min
for applying, g/L
solution, min
3
5
2000
1000
500
0.4
0.4
0.5
0.2
0.4
0.6
0.4
0.6
240
240
120
120
180
240
240
240
53
64
4
4
5
5
6
6
5
4
92.98
92.94
92.99
93.01
92.63
93.12
92.98
93.26
8
91
12
12
12
13
15
500
122
128
120
105
61
1500
500
500
500
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 4–9

NOVEL AQUEOUS SOLUBLE COBALT(II) PHTHALOCYANINES OF TETRACARBOXYL-SUBSTITUTED
5
surface was effected by subjecting the sample of polymer
recommended in [53]. They were kept under vacuum prior
to use.
The salts were prepared by recrystallization followed
by vacuum drying [54]. Acids (sulfuric and nitric) of a
special chemical grade were used without any additional
treatments.
to microwave radiation, as described in the experimental
part. Condition monitoring metallophthalocyanine after
immobilization was performed using UV-vis spectra. For
this was the chosen medium (quinoline), the refractive
index of light which is almost equal to the refractive
index of the support matrix. As can be seen from Fig. 5
macrocycle when immobilized on the surface of the
polymer matrix of the associated switches in the
monomeric state. For comparison, data for heterogeneous
catalysis with homogeneous catalysis the catalyst weight
was chosen so that the concentration was the same
macrocycle. Effective constants of DTC oxidation rates
as a function of parameters of activation of a solid-phase
carrier are presented in Table 1.
During heterogenization of CoPc(S–C6H4–COOH)4,
the question is to be solved relative to the increase of
the portion of the catalyst accessible for interaction
with the reagents. Heterogeneous catalysts based on
CoPc(S–C6H4–COOH)4 and Lavsan demonstrate higher
catalytic activity as compared with homogeneous ones.
Heterogeneous CoPc(S–C6H4–COOH)4-Lavsan catalyst
underwent testing in a series of repeated catalytic
experiments, its activity during 20 step-by-step cycles
decreasing by 3% only. Coordination mechanism is most
probably realized during heterogeneous catalysis, as
a macrocycle applied on the polymer is predominantly
monomeric.
Equipment
Electron adsorption spectra (UV-vis) were registered
by means of Shimadzu UV-1800 (Japan) double-beam
spectrophotometer in a spectral range of 190–1100 nm.
Quarts optical cell were used for the measurements.
UV-vis spectra were recorded at 298.15 0.03 K.
FT-IR spectra were recorded using IR-Fourier
spectrophotometer Avatar 360 in 400–4000 cm-1
frequency range.
1H NMR spectra of the solutions were recorded by
means of NMR spectrometer Bruker AVANCE-500 at
operating frequency 500 MHz. Measurements were
performed under the Fourier transformation conditions
in 5 mm cells at various temperatures. Chemical shifts
were measured with reference to the internal standard-
tetramethylsilane. The accuracy of measurements was
0.005 ppm.
Elemental analysis has been carried out by means of
chromatographic analyzer Flash HCNS-OEA 1112. The
flowrates of helium and oxygen were 140 mL/min and
250 mL/min, respectively; the temperature of the reactor
was 1173 K, oxygen was supplied into the reactor for
250 mL/min with 12 s time delay.
EXPERIMENTAL
Synthesis of phthalocyanine catalysts
Materials and reagents
Synthesis of 4-nitrophthalonitrile. Synthesis of
phthalonitrile is a multi-stage process which includes
nitration of phthalimide with a mixture of concentrated
sulfuric and nitric acids followed by the amidation of
4-nitrophthalimide with concentrated water solution of
ammonium hydroxide and dehydration of the resulting
diamide by thionyl chloride in DMF medium [55].
Commercial non-woven polyethylene terephthalate
(Lavsan) was used as a solid-phase carrier. It was
produced in Russia and had average molecular mass of
20 000 and specific density of 203 g/m².
Organic solvents, namely: pyridine (Py), quinoline,
N,N-dimethylformamide (DMF), chloroform, dimethyl-
sulfoxide (DMSO), were purified according to the methods
O
O
O
O2N
HNO3
NO2
O2N
SOCl2
CN
CN
NH3
NH2
NH2
NH
O
NH
O
O
1
Synthesis of 4-[(4′-carboxyl)phenylamino]phthalonitrile[4-(3,4-dicyanophenylamino)benzoic acid]].
H
NO2
H2N
COOH
NC
NC
NC
NC
N
COOH
1
2
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 5–9

6
A. VASHURIN ET AL.
10 moles of 4-nitrophthalonitrile, 10 mol of 4-amino-
benzoic acid, 20 mmol of potassium carbonate and
25 mL of DMSO were placed in a flask with a stirrer,
thermometer and reflux condenser. The reaction mixture
was heated to 358–368 K and kept at this temperature
for 5–6 h. The resulting mass was poured into water,
acidified with hydrochloric acid to form a weak-acid
medium, the resulting residue was filtered and then the
desired product was extracted from the filtrate with
chloroform and dried in vacuum at 313 K. Yield 75.6%;
mp 445 K. Anal. calcd. for C15H9O2N3: C, 68.44; H,
3.45; N, 15.96%. Found C, 68.25; H, 3.61, N, 15.85%.
¹H NMR (Py-d6): d, ppm 8.54d (1H (2)), 7.90s (1H (3)),
7.82d (1H (1)), 7.72d (2H (4,5), Ar-H), 7.29d (2H (6,7),
Ar-H). IR (KBr): n, cm-1 2237 (C≡N), 1693 (COOH),
1603 (Ar-COO), 1313, 3265 (NH).
Synthesis of 4-[(4′-carboxyl)phenylsulphonyl]phthalonitrile[4-(3,4-dicyanophenylsulphonyl)benzoic acid].
NO2
HS
COOH
NC
NC
NC
NC
S
COOH
1
3
The flask fitted with a stirrer, thermometer and
reflux condenser was filled with 0.0173 mol of 4-nitro-
phthalonitrile, 0.0173 mol of 4-mercaptobenzoic acid,
4.79 g 0.0347 mol of anhydrous K2CO3 and 52 mL of
DMF. The resulting mixture was stirred at 358–368 K
for 6 h. After cooling down to room temperature, the
reaction mixture was poured into 100 mL of distilled
water, acidified with hydrochloric acid and filtered. The
resulting residue was washed up to a neutral medium and
dried in vacuum at 313 K. Yield 80%; mp 174 K. Anal.
calcd. for C15H8N2O2S: C, 64.28; H, 2.88; N, 9.99; S,
11.44%. Found C, 63.70; H, 3.11; N, 9.85; S, 11.05%.
¹H NMR (Py-d6): d, ppm 8.54d (1H (2)), 8.41d (1H (1)),
7.86s (1H (3)), 7.81d (2H, Ar-H), 7.53d (2H, Ar-H).
IR (KBr): n, cm-1 2231 (C≡N), 1697 (COOH), 1582
(Ar-COO), 1126 (Ar-S-Ar).
Synthesis of tetrasubstituted metallophthalocyanines
X
N
COOH
COOH
X
N
N
X
COOH
Co(OAc)2
NC
NC
X
N
Co
N
N
COOH
180-185 °C
N
N
2, 3
X = S, X = NH
HOOC
X
Synthesis of phthalocyanine from phthalonitriles
prepared as described above was carried out using the
procedure given in [56, 57].
the following composition: C 60.34; H 3.45; N 8.97; S
10.28. Theoretical composition of C60H32CoN8O8S4 is the
following: C 61.07%; H 2.73%; N 9.49%; S 10.87%.
The yield of cobalt tetra-4-[(4′-carboxyl)phenylamino]
phthalocyanine (CoPc(NH–C6H4–COOH)4) was 56.9%.
Elemental analysis showed the following composition: C
63.92%; H 3.47%; N 14.73%. Theoretical composition
of C60H36CoO8N12 is the following: C 64.81%; H 3.26%;
N 15.12%.
For cobalt tetra-4-[(4′-phenylsulfonyl)carboxyl]phtha-
locyanine (CoPc(S–C6H4–COOH)4 the yield of the
target product was 85%. Elemental analysis showed
Formation of phthalocyanine complexes
with pyridine
While adding pyridine to the water solution of
metallophthalocyanine (at 298.15 K), the following
equilibrium is reached:
ꢀꢀꢁ
(10)
MPc + L
(L)⋅MPc
ꢂꢀꢀ
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 6–9

NOVEL AQUEOUS SOLUBLE COBALT(II) PHTHALOCYANINES OF TETRACARBOXYL-SUBSTITUTED
7
Stability constants of molecular complexes were
calculated from the equation:
copper complex with DTC formed immediately. The
precipitate was extracted with chloroform. To increase
the accuracy of the analysis and insure that all complex
was collected from the aqueous solution the extraction
process was repeated. An organic layer was transferred
into a 25 mL volumetric flask, which was then filled
to the mark with chloroform. Optical density of the
solution was determined by spectrophotometric method
at wavelength of 436 nm. DTC concentration was
calculated using a known molar extinction coefficient for
copper DTC complex which was earlier determined by
calibration (e = 35.32 l/(mol.cm)).
Ky = [(L)⋅MPc] /([MPc]⋅[L])
(11)
Equilibrium concentrations of a molecular complex
were calculated as:
c(L)⋅MPc = cM0 Pc ⋅(A0 − Ap) /(A0 − Ak)
(12)
where c(L)•MPc is equilibrium (L)·MPc concentration, c0MPc
is an initial MPc concentration, A0, Ap, Ak — are initial,
equilibrium and final optical density of the solution,
respectively.
The conversion was calculated from the equation:
Ligand concentration was determined from the
equation:
c = (c0 − ct ) /c0
(16)
cL = cL0 − cM0 Pc ⋅(A0 − Ap) /(A0 − Ak)
where c0 — initial concentration of DTC, ct — DTC
concentration at the current time.
(13)
Combining Equations 11 and 12 leads to the following
equation for stability constant:
Heterogenization of phthalocyanines on polymer
Ky = [( A0 − Ap) / ( Ap − Ak)] /[cL0 − cM0 Pc⋅ ( A0 − AP ) / ( A0 − Ak ) ]
10 × 10 cm sample of non-woven Lavsan was subjected
to microwave radiation for 3–15 min at 2450 MHz
frequency and 500–2000 W power. Then the sample
was immersed into water-alkaline solution (pH 10) of
metallophthalocyanine with concentration of 0.2–0.6 g/L
and kept there for 2–4 h at room temperature. Finally the
sample was treated in 100 mL of NaOH aqueous solution
with pH 8.0–8.5 for 40 min.
(14)
Since the titration was done from the mole ratio of 1 to
10 up to the extraligand being in excess by a factor of 100
the equation for the stability constant can be simplified
as follows:
Ky = (A0 − Ap) /[(Ap − Ak)⋅ cL0 ]
(15)
Oxidation of sodium diethyldithiocarbamate
CONCLUSION
Experiments to study the kinetics of oxidation reaction
of sodium diethylthiocarbamate (DTC) with ambient
oxygen were carried out in a thermostatic unit, in which
650 mL of DTC solution were placed. The process of
oxidation of DTC can be represented by the following
general scheme:
Two new water-soluble carboxyl peripherally
substitutedcobalt(II)phthalocyanineshavebeenprepared.
It has been shown that bonding of –COOH groups with
phthalocyanine cycle through the spacer containing
–NH groups, favors the formation of monomeric forms
of phthalocyanine in the solution. Bonding of ionogenic
groups with phthalocyanine cycle through the spacer
containing –S groups, favors the formation of dimeric
forms of phthalocyanine in the aqueous solution.
Stable monomeric form of CoPc(NH–C6H4–COOH)4
macrocycle possesses negligible catalytic activity in
homogeneous catalysis, whereas macrocycles available
in the solution in a labile dimeric form are catalytically
active.
C2H5
C2H5
C2H5
C2H5
S
S
S
S
C2H5
C2H5
SH
O2, catalyst
-2Na
2
N
C
C N
Na
N C
S
Air was pumped using a microcompressor at 2 l/min
flow rate. Under these conditions, the reaction goes in
kinetic mode. After reaching the constant temperature,
the reaction mixture was stirred; 2 mL sample was taken
to determine the initial DTC concentration, after that the
compressor was switched back on again. The moment
when the air was pumped in was taken as the beginning
of the reaction. During the experiment, 2 mL samples
were periodically taken to determine DTC current
concentration.
The immobilization of CoPc(S–C6H4–COOH)4 on
polymers enhances their catalytic activity in the oxidation
of sodium diethyldithiocarbamate by air oxygen under
mild conditions.
Thefollowingproceduretodeterminetheconcentration
of DTC was used: 2 mL sample was placed in a 25 mL
flask and then 4 mL of the aqueous CuSO4 solution (c =
0.05 M) were added. A thick, dark-brown precipitate of
Acknowledgements
The reported study was supported by Russian Science
Foundation (grant number 14-23-00204).
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 7–9

8
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