Synthesis and Properties of Cobalt(II) Tetrakis-[4,5-di(4′-carboxy)phenylene(oxy/sulfanyl/amino)]phthalocyanines

Article abstract of DOI:10.1134/S1070363218090451

Phthalonitriles with fragments of 4-hydroxy, 4-mercapto and 4-aminobenzoic acids were synthesized by nucleophilic substitution in 4-bromo-5-nitrophthalonitrile. The synthesized phthalonitriles were used to prepare octasubstituted cobalt phthalocyanines by

Full text of DOI:10.1134/S1070363218090451

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 9, pp. 2020–2027. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.P. Morozova, S.A. Znoiko, A.S. Vashurin, A.V. Zav’yalov, V.E. Maizlish, G.P. Shaposhnikov, 2016, published in Rossiiskii
Khimicheskii Zhurnal, 2016, Vol. 60, No. 2, pp. 80–88.
Synthesis and Properties of Cobalt(II) Tetrakis-
[4,5-di(4'-carboxy)phenylene(oxy/sulfanyl/amino)]phthalocyanines
A. P. Morozovaa , S. A. Znoikoa**, A. S. Vashurina***, A. V. Zav’yalova****
* ,
V. E. Maizlisha*****, and G. P. Shaposhnikova******
a Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology,
Sheremetevskii pr. 7, Ivanovo, 153000 Russia
e-mail: *asya_morozova@mail.ru; **znoykosa@yandex.ru; ***asvashurin@mail.ru; ****zav2003@inbox.ru;
*****maizlish@isuct.ru; ******ttoc@isuct.ru
Received January 15, 2016
Abstract―Phthalonitriles with fragments of 4-hydroxy, 4-mercapto and 4-aminobenzoic acids were
synthesized by nucleophilic substitution in 4-bromo-5-nitrophthalonitrile. The synthesized phthalonitriles were
used to prepare octasubstituted cobalt phthalocyanines by template synthesis. The spectral properties of the
products were studied.
Keywords: 4-bromo-5-nitrophthalonitrile, benzoic acids, metal phthalocyanines, electronic absorption spectra
DOI: 10.1134/S1070363218090451
Carboxylic acids and their derivatives occupy special
place among numerous substituted phthalocyanines
because of their diverse potential uses in science and
technics [1‒10]. Over the past years phthalocyanines
containing as substituents hydroxy- [1, 5, 8–10], amino
[7,9], or mercaptobezoic acids [6, 9] have attracted
attention of scientists and practitioners. It was found
that some of such substituted macroheterocyclic com-
pounds can find application as liquid crystalline [5]
and medical materials [11], dyes and photo-sensitizers
[6, 7, 12], as well as catalysts [13, 14]. Therewith, all
publications dealt with either tetrasub-stituted phthalo-
cyanines [1, 5–8, 13, 14] or octasubstituted phthalo-
cyanines with 3,5-dicarboxyphenoxy fragments [2‒4].
stituents para-substituted benzoic acid fragments and
studied their spectral properties.
The starting 4,5-bis(4-carboxyphenoxy)- (2), 4,5-
bis[(4-carboxyphenyl)sulfanyl]– (3), and 4,5-bis[4-
carboxyphenyl)amino]phthalonitriles (4) were syn-
thesized by the nucleophilic substitution of the bromo
and nitro groups in 4-bromo-5-nitrophthalonitrile (1)
by corresponding benzoic acid residues (Scheme 1).
Like with other disubstituted phthalonitriles [1, 9], the
synthesis was performed in aqueous DMF in the
presence of potash. Since in the present work we
substituted both the Br and NO2 groups, the reaction
mixture was heated at 80‒90°С for 18‒24 h. In the
case of compound 4 containing para-aminobenzoic
acid residues as substituents, the reaction was per-
formed in the presence of trimethylamine.
In the present work we synthesized 4,5-octa-
substituted cobalt phthalocyanines containing as sub-
Scheme 1.
COOH
HX
X
X
CN
CN
HOOC
HOOC
Br
CN
CN
O2N
1
2−4
X = O (2), S (3), NH (4).
2020

SYNTHESIS AND PROPERTIES OF COBALT(II)
Table 1. Signal positions in the 1H NMR spectra of compounds 2‒4
2021
NC
CN
1'
1
2' 3'
3
2
X
X
COOH
HOOC
Signal position, δ, ppm
X= S (3)
Atom no.
X = O (2)
X= NH (4)
experiment
theory
7.75
experiment
7.66
theory
7.89
experiment
7.88
theory
8.08
H1,1'
H2,2'
8.01
6.96–7.00
6.96–7.06
7.59–7.61
7.57–7.60 d
7.08–7.09
7.52–7.53
J = 2.01 Hz
J = 2.05 Hz
J = 2.05 Hz
H3,3'
8.05–8.09
11.72
8.03–8.12 d
J = 2.05 Hz
8.08–8.10
7.96–8.02 d
J = 2.04 Hz
7.73–7.76
7.62–7.63 d
J = 2.01 Hz
COOH
NH
10.58 s
11.72
–
10.55 s
8.49
8.49
8.58 s
8.51 s
Compounds 2 and 3 can also be synthesized by
introducing the second benzoic acid to presynthesized
4-(4'-carboxyphenylsulfanyl)-5-nirophthalonitrile or 4-
(4'-carboxyphenoxy)-5-nitrophthalonitrile [9]. Therewith,
the two-stage synthesis requires isolation of the
intermediate product, which increases the synthesis
time and entails additional losses on purification. We
failed to synthesize compound 4 from 4-(4'-carboxy-
phenylamino)-5-nitrophthalonitrile.
which reveals itself in a red shift of this band,
increasing the following order of bridging groups:
3 (X = S) < 4 (X = NH) < 2 (X = O).
The dependence of the ν(C≡N) band position on the
nature of the bridging group was also observed in our
previous work [9], where we synthesized
phthalonitriles having the nitro group ortho to the
corresponding benzoic acid fragment. However, in that
case the red shift of this band varied in a different
order of bridging groups:
To isolate compounds 2 and 3, the reaction mixture
was poured into 5% aqueous HCl, and the precipitate
that formed was filtered off and washed with acidic
water. The yields of compounds 2 and 3 were 72 and
88%, respectively.
(X = O) < (X = S) < (X = NH) [9].
Furthermore, the spectra of all the synthesized
compounds display the ν(O–H) and ν(С=О) bands of
the carboxyl groups of the benzoic acid fragments at
3417‒3457 and 1706‒1710 cm–1, respectively [15].
The spectra of compounds 2‒4 show no symmetric
(1342‒1352 cm–1) and antisymmetric (1562‒1565 cm–1)
vibration bands of the N=O bonds of the nitro groups
[15], providing evidence for completion of
nucleophilic substitution of the NO2 group in
compound 1. The spectrum of phthalonitrile 3 contains
the stretching vibration band of the Ar–S–Ar group at
1104 cm–1 [15], and the spectrum of phthalonitrile 4,
which contains a para-aminobenzoic acid fragment,
shows the stretching (3195 cm–1) and deformation
(1604 cm–1) vibration bands of the N–H bond of the
secondary amino group. The spectrum of compound 2
In the case of phthalonitrile 4, the reaction mixture
were poured into water, the target product was
extracted with chloroform, and the organic layer was
subjected to column chromatography on silica gel
(eluent chloroform). The eluate was then evaporated,
and phthalonitrile 4 was dried under vacuum at 70°С.
The yield of the target product was 40%.
Compounds 2‒4 were identified by elemental
1
analysis, UV-Vis, Н NMR, and IR spectroscopy, and
MALDI-TOF mass spectrometry.
The IR spectra of all the products contain the
ν(C≡N) band at 2229‒2237 cm–1 [15]. The position of
this band depends on the nature of the bridging group,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

2022
MOROZOVA et al.
Scheme 2.
HOOC
COOH
X
X
COOH
COOH
COOH
N
N
N
Co
N
NC
NC
X
X
X
X
X
ο
.
CoCl2 6H2O, 160−170 C
N
N
X
N
N
COOH
COOH
HOOC
COOH
COOH
X
X
5−7
2−4
X = O (2, 5), S (3, 6), NH (4, 7).
displays the stretching vibration band of the Ar–O–Ar
band at 1220 cm–1 [15].
from the MALDI‒TOF mass spectra, which contain
molecular ion peaks at m/z 399 (2), 431 (3), and 398
(4) (Fig. 1).
1
The positions of signals in the Н NMR spectra of
compounds 2‒4 in DMSO-d6 are listed in Table 1.
After isolation and identification the synthesized
phthalonitriles were used as starting materials to obtain
octasubstituted cobalt phthalocyanines 5−7.
1
The Н NMR spectra of compounds 2‒4 display a
downfield signal of the phthalonitrile benzene rings
(Table 1). The position of this signal depends on the
nature of the bridging group (Table 1) and shifta
upfield in the following order:
The synthesis was performed by the nitrile method,
specifically, by heating the corresponding substituted
phthalonitrile and cobalt chloride in the presence of
urea at 160−170°С until the reaction mixture solidified
(Scheme 2). After cooling down the solid material was
ground and transferred onto a filter, successively
washed with acidified water and acetone, and dried.
The target compounds were extracted with DMF, and
the solvent was removed to leave dry dark green
powders insoluble in acetone and chloroform, readily
soluble in water and aqueous alkaline solutions, and
sparingly soluble in DMF.
4 (X = NH) < 3 (X = S) < 2 (X = O).
The downfield signals in the range 7.52‒8.12 ppm
belong to the benzene ring protons of the benzoic acid
residues.
1
The COOH proton signals in the Н NMR spectra
of compounds 2‒4 are observed at 8.58‒10.58 ppm.
This fact implies that the target phthalonitriles are
carboxylic acids rather than salts. The spectrum of
compound 4, which has two para-aminobenzoic acid
fragments ortho to each other, shows a downfield
(8.51 ppm) two-proton signal of the secondary amino
group. The position of the benzene ring signals of the
benzoic acid fragments located ortho to the bridging
group, too, depend on the nature of this group. Thus,
the signals shift upfield in the following order:
Compounds 5‒7 were identified by elemental
analysis, UV-Vis and IR spectroscopy, and MALDI-
TOF. mass spectrometry.
The mass spectral data are presented in Experi-
mental and Fig. 2.
The IR spectra of the synthesized cobalt phthalo-
cyanines show no ν(C≡N) band at 2225‒2240 cm–1
[15], which suggests a lack of impurities of the starting
compounds. The spectra of all of the synthesized
3 (X = S) < 4 (X = NH) < 2 (X = O) (Table 1).
Further evidence showing that compounds 2‒4 are
carboxylic acids rather than potassium salts comes
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

SYNTHESIS AND PROPERTIES OF COBALT(II)
2023
399.2978 (r2819)
COOH
100
80
(a)
O
O
CN
CN
60
40
400.2935 (r2759)
20 64.2334 (r2303)
424.3581 (r2582)
COOH
520.4195 (r3050)
Mr = 400.35
0
400
600
800
1000
1200
m/z
1400
1600
1800
431.2840 (r3003)
COOH
100
80
60
40
20
0
(b)
S
S
CN
CN
469.2902 (r3078)
COOH
Mr = 432.47
400
600
800
1000
1200
m/z
1400
1600
1800
Fig. 1. MALDI-TOF mass spectra of compounds (а) 2 and (b) 3.
phthalocyanines contain the stretching vibration bands
of the functional groups, which were also observed in
the IR spectra of phthalonitriles 2‒4. Therefore, we can
conclude that phthalocyanines 5‒7 contain the same
functional groups.
that, at equal concentrations of DMF solutions, the red
shift of the Q band decreases in the following order of
compounds:
6 (X = S) < 5 (X = O) < 7 (X = NH).
Analyzing the spectral patterns (Fig. 2), we can
draw a preliminary conclusion that the cobalt
phthalocyanine containing mercaptobenzoic acid
fragments (compound 6) has the highest degree of
association in DMF.
Analyzing the UV-Vis spectra of compounds 5‒7
both in aqueous alkali and in DMF we can note that
the spectral curves are diffuse. Moreover, the Lambert
‒Bouguer‒Beer law fails in this case. Consequently,
cobalt phthalocyanines are present mostly in the
associated form. The positions of the longwave
absorption bands depend on the nature of the bridging
heteroatom Х (Table 2, Fig. 3). Thus, it was found
Diffuse longwave bands (λmax 650‒705 nm) are also
observed in the UV-Vis spectra of aqueous alkaline
solutions (5% aqueous ammonia), even when their
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

2024
100
MOROZOVA et al.
1676.3152 (r436)
1674.6234 (r284)
80
60
1886.8696 (r329)
1856.4025 (r301)
1896.9301 (r269)
40
20
2097.0263 (r348)
2117.6522 (r54)
2399.9449 (r154)
2598.4548 (r60)
2831.1422 (r97)
0
1600
1800
2000
2200
2400
2600
2800
3000
m/z
Fig. 2. Fragment of the MALDI-TOF mass spectrum of compound 5 in the m/z range 1600‒3000.
concentrations are quite low (10–6‒10–3 M) (Fig. 4,
Table 2). The spectra of phthalocyanines 6 and 7,
which contain 8 fragments of p-mercaptobenzoic and
p-aminobenzoic acid fragments, display two maxima
of equal intensity in the first case and with a much
stronger longwave component in the second (Table 2).
As previously [1, 9], the position of the Q band and
its red shift in going from DMF to conc. H2SO4 depend
on the nature of the heteroatom bridging the benzoic
acid and phthalocyanine components. The red shift of
the Q band decreases in the following order (Table 2):
(6, X=S) > (7, X = NH) > (5, X = O).
In going to aqueous alkaline and organic solvents to
conc. H2SO4, the longwave bands shift red (Table 2,
Fig. 5). The replacement of the nitro group in cobalt
tetra-4-(4'-carboxyphenylsulfanyl)-tetra-5-nitrophthalo-
cyanine [9] by one more mercaprobenzoic acid
fragment shifts the longwave absorption band in the
UV-Vis spectrum in conc. H2SO4 by 180 nm (Table 2).
In the case of compounds with hydroxyl- and amino-
benzoic acid fragments such shift is not so large (40
and 22 nm, respectively).
Thus, the nucleophilic substitution of bromine in
4-bromo-5-nitrophthalonitrile by benzoic acid fragments
allowed us to synthesize phthalonitrile containing 2
identical benzoic acid fragments located ortho to each
other. The tetramerization of the synthesized phthalo-
nitriles with cobalt chloride gave novel octasubstituted
cobalt phthalocyanines.
The spectral properties of the synthesized com-
pounds were studied. It was found that the position of
687
D
680
D
660
671
699
0.30
1
2
3
0.40
673
2
1
0.20
0.10
0.00
0.20
0.00
500
600
700
800 λ, nm
500
600
700
800 λ, nm
Fig. 4. Electronic absorption spectra of compounds (1) 5
and (2) 6 in 5 % aqueous NH4OH (0.55×10–5 M).
Fig. 3. Electronic absorption spectra of compounds (1) 5,
(2) 6, and (3) 7 in DMF (0.45×10–5 M).
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SYNTHESIS AND PROPERTIES OF COBALT(II)
2025
Table 2. Positions of the longwave absorption bands in the
UV-Vis spectra of compounds 5‒7 in different solvents
the Q band and its red shift in going from DMF to
conc. H2SO4 depends on the nature of the heteroatom
bridging the benzoic acid and phthalocyanine
fragments. The red shift of the Q band decreases in the
following order:
UV-Vis spectrum, λmax (intensity ratio)
Comp.
no.
X
DMF
680
NH4OH (5%)
671
H2SO4
813
5
6
O
S
(7, X=S) > (8, X = NH) > (6, X = O).
673
660; 699
993
Similar trends we previously observed in the
spectra of cobalt phthalocyanines combining the cor-
responding benzoic acid fragments and nitro groups [9].
(1.00 : 0.97)
7
NH
687
651; 701
829
(1.00 : 1.75)
EXPERIMENTAL
necked flask equipped with a reflux condenser. The
resulting mixture was diluted with water, heated with
stirring at 80‒90°С for 24 h, and poured into acidified
water. The solid target product was filtered off and
washed with 5% aqueous HCl until colorless washings.
All analyses were performed using the equipment
of the Center for Collective Use, Ivanovo State
University of Chemical Technology.
Elemental analysis was performed on on a Thermo
Scientific FlashEA 1112 CHNS-O analyzer.
4,4'-(4,5-Dicyano-1,2-phenylenedioxy)dibenzoic
acid (2) was synthesized from 2.76 g of para-
hydroxybenzoic acid. After the reaction had been
complete, the reaction mixture was poured into 5%
aqueous HCl, the precipitate that formed was filtered
off, washed with 2% aqueous HCl, and dried in air at
70‒80°С. Yield: 2.88 g (72% per 1). Found, %:C
64.59; H 3.12; N 6.83. C22H12N2O6; Calculated, %: C
66.00; H 3.02; N 7.00. Mass spectrum, m/z: 399.30
[M ‒ Н]–; calculated М 400.07. IR spectrum, ν, cm–1:
3457 (ОН); 2237 (C≡N); 1708 (C=O); 1220 (Ar–O–
Ar). 1Н NMR spectrum, δ, ppm: 10.58 s (СООН, 2Н);
7.66 s (Н1, 2Н); 6.96‒7.06 d (Н2, 4Н, J = 2.01 Hz);
8.03‒8.12 d (Н3, 4Н, J = 2.05 Hz).
The UV-Vis spectra were registered in DMF, aqueous
ammonia, and conc. H2SO4 on a Hitachi U-2001
spectrophotometer at room temperature in the range
400‒900 nm. The IR spectra were run in KBr pellets
on an Avatar 360 FT-IR ESP spectrometer in the range
400‒4000 cm–1.
1
The Н NMR spectra were measured on a Bruker
DRX-500 instrument in DMSO-d6 against internal
TMS.
The MALDI-TOF mass spectra were obtained on a
Shimadzu Biotech Axima Confidence instrument in
the negative (2, 3) and positive (4‒7) ion modes using
α-cyano-4-hydroxycinnamic acid as a matrix. The
samples were prepared by mixing solutions of com-
pounds 2–4 in THF (с = 10–4–10–5 M) or compounds
4–9 in DMF with a solution of the matrix (30 mg/mL)
in THF.
4,4'-(4,5-Dicyano-1,2-phenylenedisulfanyl)di-
benzoic acid (3) was synthesized from 3.08 g of para-
mercaptobenzoic acid and isolated by acidifying the
993
D
813
4-Bromo-5-nitrophthalonitrile (1) was syn-
thesized by the procedure described in [16]. The
physicochemical characteristics of this product were
well consistent with published data: mp 140‒142°С.
Found, %: 38.10; N 16.50; Н 0.76. C8H2BrN3O2.
Calculated, %: C 38.16; N 16.67; Н 0.80.
2
1
0.40
0.20
Synthesis of 4,4'-[4,5-Dicyano-1,2-phenylenedi-
(oxy/sulfanyl/amino)]dibenzoic acids (2‒4). Method
1 (general procedure). A solution of 5.52 g (0.04 mol)
of anhydrous potassium carbonate in 7 mL of water
was added to a solution of 2.52 g (0.01 mol) of
4-bromo-5-nitrophthalonitrile (1) and 0.02 mol of
corresponding benzoic acid in 50 mL of DMF in a two-
0.00
500
600
700
800
900 λ, nm
Fig. 5. Electronic absorption spectra of compounds (1) 5
and (2) 6 in H2SO4.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

2026
MOROZOVA et al.
reaction mixture with 5% aqueous HCl, filtering off
the precipitate that formed, washing it with 2%
aqueous HCl, and drying in air at 70‒80°С. Yield: 3.80 g
(88% per 1). Found, %: C 60.95; H 2.93; N 6.15; S
14.35. C22H12N2O4S2. Calculated%: C 61.10; H 2.80;
N 6.48; S 14.83. Mass spectrum, m/z: 431.28 [M ‒ Н]–;
calculated М 432.02. IR spectrum, ν, cm–1: 3417 (ОН);
off, washed with 2% aqueous HCl, and dried in air at
70‒80°С. Yield 0.21 g (51% per 1). Found, %: C
64.63; H 3.14; N 6.67; C22H12N2O6; Calculated, %: C
66.00; H 3.02; N 7.00. IR spectrum, ν, cm–1: 3454
(ОН); 2237 (C≡N); 1708 (C=O); 1220 (Ar–O–Ar).
4,4'-(4,5-Dicyano-1,2-phenylenedisulfanyl)di-
benzoic acid (3) was synthesized from 0.33 g of 4-(4,5-
dicyano-2-nitrophenoxy)benzoic acid and 0.15 g of
para-mercaptobenzoic acid. After the reaction had
been complete, the reaction mixture was acidified with
5% aqueous HCl, the precipitate that formed was
filtered off, washed with 2% aqueous HCl, and dried in
air at 70‒80°С. Yield 0.27 g (62% per 1). Found, %: C
60.90; H 2.90; N 6.24; S 14.52; C22H12N2O4S2; Cal-
culated, %: C 61.10; H 2.80; N 6.48; S 14.83. IR
spectrum, ν, cm–1: 3417 (ОН); 2229 (C≡N); 1710
(C=O); 1104 (Ar–S–Ar).
1
2229 (C≡N); 1710 (C=O); 1104 (Ar–S–Ar). Н NMR
spectrum, δ, ppm: 10.55 s (СООН, 2Н); 7,88 s (Н1,
2Н); 7.57–7.60 d (Н2, 4Н; J = 2,05 Hz); 7.96–8.02 d
(Н3, 4Н; J = 2.04 Hz).
4,4'-(4,5-Dicyano-1,2-phenylenediamino)dibenzoic
acid (4) was prepared from 2.74 g of para-amino-
benzoic acid in the presence of 2 mL of trimethyl-
amine. After the reaction had been complete, the
reaction mixture was poured into water and diluted
with chloroform. The chloroform layer was separated,
and the solvent was removed by distillation. The
residue was subjected to column chromatography on
silica gel, eluent chloroform. The solvent was removed
by distillation, and the product was dried in a vacuum
at 70°С. Yield: 1.59 g (40% per 1). Found, %: C
65.20; H 3.33; N 14.10; C22H14N4O4; Calculated %: C
66.33; H 3.54; N 14.06. Mass spectrum, m/z: 398.96
[M + Н]+; calculated М 398.38. IR spectrum, ν, cm–1:
3418 (ОН); 3195 (NH); 2234 (C≡N); 1706 (C=O);
Synthesis of cobalt octa-[4,5-(4-carboxyphenyl
(oxy/sulfanyl/amino)]phthalocyanines 5‒7 (general
procedure). A fine mixture of 0.33 mmol of cor-
responding substituted phthalonitile, 54 mg (0.20 mmol)
of cobalt chloride tetrahydrate, and 60 mg (1 mmol) of
urea was heated at 160‒170°С until solidification, after
which it was ground, washed with acidified water and
acetone, and dried in air at 70‒80°С.
1
1604 [δ(NHsec)], [ν(NHsec)]. Н NMR spectrum, δ,
ppm: 8.58 s (СООН, 2Н); 8.51 s (NН, 2Н); 8.01 s (Н1,
2Н); 7.52‒7,53 d (Н2, 1Н; J = 2.05 Hz); 7.62‒7.63 d
(Н3, 2Н; J = 2.01 Hz).
Cobalt octa-[4,5-(4-carboxyphenoxy)]phthalo-
cyanine (5) was synthesized from 120 mg of phthalo-
nitrile 2. Yield 82 mg (68%). Found, %: C 63.10; H
3.04; N 6.55; C88H48N8O24Со; Calculated, %: C 63.66;
H 2.91; N 6.75. Mass spectrum, m/z: 1676.17 [M + О]+;
calculated 1660.32. IR spectrum, ν, cm–1: 3443 (OH);
1712 (C=O); 1224 (Ar–O–Ar).
Method 2 (general procedure). A solution of 0.14 g
(0.1 mmol) of anhydrous potassium carbonate in
0.7 mL of water was added to a solution of 0.1 mmol
of 4-(4,5-dicyano-2-nitrophenoxy)-, 4-(4,5-dicyano-2-
nitrophenylsulfanyl)-, and 4-(4,5-dicyano-2-nitrophenyl-
amino)benzoic acid, and 0.1 mmol of corresponding
benzoic acid in 5 mL DMF in a two-necked flask
equipped with a reflux condenser. The reaction
mixture was stirred at 80‒90°С for 24 h. The pre-
cipitate that formed was filtered off, washed with 5%
aqueous HCl until colorless washings, and dried in air
at 70‒80°С.
Cobalt
octa-[4,5-(4-carboxyphenylsulfanyl)]-
phthalocyanine (6) was synthesized from 130 mg of
phthalonitrile 3. Yield 95 mg (73%). Found, %: C
59.17; H 2.82; N 6.10; C88H48N8O16S8Со. Calculated,
%: C 59.09; H 2.70; N 6.26. Mass spectrum, m/z:
1789.78 [M + Н]+; calculated М 1788.81. IR spectrum,
ν, cm–1: 3447 (ОН), 1711 (C=O), 1104 (Ar–S–Ar).
Cobalt
octa-[4,5-(4-carboxyphenylamino)]-
Compound 4 could not be prepared by this method.
phthalocyanine (7) was synthesized from 120 mg of
phthalonitrile 4. Yield 49.4 mg (41%). Found, %: C
63.70; H 3.55; N 13.18. C88H56N16O16Со. Calculated,
%: C 63.96; H 3.42; N 13.56. Mass spectrum, m/z:
1652.36 [M + 4H]+, calculated М 1651,33. IR spec-
trum, ν, cm–1: 3413 (ОН); 3172 (NH); 1703 (C=O);
1602 [δ(NHsec)]; 1434 [ν(NHsec)].
4,4'-(4,5-Dicyano-1,2-phenylenedioxy)dibenzoic
acid (2) was synthesized from 0.31 g of 4-(4,5-dicyano-
2-nitrophenoxy)benzoic acid and 0.14 g of para-
hydroxybenzoic acid. After the reaction had been
complete, the reaction mixture was poured into 5%
aqueous HCl, the precipitate that formed was filtered
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

SYNTHESIS AND PROPERTIES OF COBALT(II)
2027
Russ. J. Gen. Chem., 2014, vol. 84, no. 1, p. 131. doi
10.1134/S1070363214010204
ACKNOWLEDGMENTS
8. Xu, H.-N., Chen, H.-J., Zheng, B.-Y., Zheng, Y.-Q.,
Ke, M.-R., and Huang, J.-D., Ultrason. Sonochem.,
2015, vol. 22, no. 1, p. 125. doi 10.1016/
j.ultsonch.2014.05.019
The work was financially supported by the Russian
Foundation for Basic Research (project no. 14-23-
00204p).
9. Morozova, A.P., Znoiko, S.A., Vashurin, A.S., Zav’ya-
lov, A.V., Maizlish, V.E., and Shaposhnikov, G.P.,
Russ. J. Gen. Chem., 2015, vol. 87, no. 12, p. 3063. doi
10.1134/S1070363217120544
10. Shaposhnikov, G.P., Maizlish, V.E., and Kulinich, V.P.,
Russ. J. Gen. Chem., 2007, vol. 77, no. 1, p. 138. doi
10.1134/S1070363207010215
11. Photosensitizers in Medicine, Environment, and Security,
Nyokong, T. and Ahsen, V., Dordrecht: Springer, 2012.
ISBN 978-90-481-3872-2.
12. Cid, J.-J., García-Iglesias, M., Yum. J.-H., Forneli, A.,
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CONFLICT OF INTERESTS
No conflict of interests was declared by the authors.
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