Synthesis and properties of 4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles and cobalt phthalocyanines obtained therefrom

Article abstract of DOI:10.1134/S1070363215120208

The diazotization-azocoupling method has been utilized to prepare a series of previously unknown 4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles, which were further transformed into the corresponding cobalt phthalocyanines. The effect of the peripheral substitution of the phthalocyanine ligand on the spectral properties of the prepared compounds has been demonstrated.

Full text of DOI:10.1134/S1070363215120208

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 12, pp. 2778–2785. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © T.V. Tikhomirova, O.M. Gruzdeva, G.P. Shaposhnikov, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 12,
pp. 2049–2056.
Synthesis and Properties
of 4-[(Е)-(4'-R-Phenyl)diazenyl]phthalonitriles
and Cobalt Phthalocyanines Obtained Therefrom
T. V. Tikhomirova, O. M. Gruzdeva, and G. P. Shaposhnikov
Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology,
Sheremetevskii pr. 7, Ivanovo, 153000 Russia
e-mail: tararjkina@mail.ru
Received April 9, 2015
Abstract—The diazotization–azocoupling method has been utilized to prepare a series of previously unknown
4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles, which were further transformed into the corresponding cobalt
phthalocyanines. The effect of the peripheral substitution of the phthalocyanine ligand on the spectral
properties of the prepared compounds has been demonstrated.
Keywords: synthesis, chromophore, diazotization, azocoupling, phthalonitrile, phthalocyanine, electron absorption
spectrum
DOI: 10.1134/S1070363215120208
Phthalocyanines (Pc) are extremely interesting
objects of fundamental and applied studies, owing to
the unique stability as well as photochemical and
electronic properties [1, 2]. Broadening of the light
absorption range (in particular, via introduction of
additional chromophore group at the periphery of the
molecule [3–5]) has been among important issues of
Pc investigations.
The dyes stability against photochemical decom-
position is generally determined by the presence of the
weak bonds (qiunoid fragments in the case of the
phthalocyanines) and labile atoms (for instance,
hydrogen atoms of amino and hydroxy groups) [10].
Hence, light resistance of the dye could be enhanced
via acylation or alkylation of the hydroxy group of
compound 3b (Scheme 2).
Our earlier studies in this direction have been des-
cribed in [6–8]; here we report on the preparation of 4-
[(E)-(4'-R-phenyl)diazenyl]nitriles 3a–3f and the
corresponding cobalt phthalocyanines 4a–4f.
In view of the poor stability of azo dyes in the hot
aqueous alkali solutions, pyridine was used to bind
hydrogen chloride evolving in the course of compound
3b acylation [11]. Alkylation of compound 3b with
different alkyl bromides was performed in a DMF–
water mixture in the presence of excess of potassium
carbonate, the latter activating the phenol group and
binding the evolving hydrogen bromide.
Starting 4-aminophthalonitrile 1 was prepared via
reduction of 4-nitrophthalonitrile with tin(II) chloride
in muriatic medium [9]. Compound 1 was further
transformed into the diazonium salt 2 via treatment
with sodium nitrite solution in aqueous sulfuric acid at
cooling below 0°C [9]. The so formed unstable salt 2
was introduced (without isolation) into the azocoupling
reaction with diphenylamine or 4-hydroxybenzoic acid
(Scheme 1).
The prepared phthalonitriles 3a–3f were red-orange
powders, readily soluble in acetone, DMF, and chloro-
form. Alkylation or acylation of the hydroxy group of
compound 3b noticeably decreased the melting point
of the modified phthalonitriles.
The pathway of the reaction with 4-hydroxybenzoic
acid (the carboxy group substitution) has been earlier
described in [10].
The prepared products were identified using the
data of elemental analysis as well as IR, 1H NMR, and
electron absorption spectroscopy [12].
2778

SYNTHESIS AND PROPERTIES OF 4-[(Е)-(4'-R-PHENYL)DIAZENYL]PHTHALONITRILES
2779
Scheme 1.
NH2
NC
NC
1
4
4
5
7
6
NH
Na2NO2,
2HCl
1
2
8
NC
NC
NH
N N
7
5
6
DMF
3
N2+Cl−
3а
NC
NC
4
5
1
2
2
HO
COOH
N N
OH
NC
NC
5
4
NaOH
3
3b
Scheme 2.
O
4
5
5
7
6
OC3H7
1
Cl
NC
NC
O
O
C
CH82CH29CH130
N N
7
O
6
4
Py
3
2
3c
3b
5
5
4
1
N
N
OR
NC
NC
BrR, K2CO3
DMF, H2O
4
3
2
3d−3f
7
7
8
8
10
11
12
CH26CH27CH82СH39 (d), CH62CH72CH82CH92CH2 CH2 СH3 (e),
R =
CH26
9
(f).
The absorbance band of nitrile group stretching
vibrations characteristic of compound 1 was preserved
in IR spectra of all prepared phthalonitriles 3a–3f
(2230–2240 cm–1); on top of that, the products spectra
contained the bands assigned to the N=N stretching
vibrations (1608–1580 cm–1) and aliphatic C–H
stretching vibrations (2848–2930 cm–1). Besides those
common bands, the spectrum of compound 3a
contained the bands at 3414 and 1614 cm–1 (stretching
vibrations and bending vibrations of the secondary
amino group, respectively) and at 1387 cm–1 (the C–N
stretching vibrations); the spectrum of phthalonitrile
3b contained the absorption bands at 3500 and
1328 cm–1 (stretching vibrations and bending
vibrations of hydroxy group, respectively); the spectra
of compounds 3c–3f contained a band at 1250–
1257 cm–1 (the С–O–С stretching vibrations); the spec-
trum of compound 3c contained an additional absorp-
tion band at 1729 cm–1 (the C=O bond stretching
vibrations).
Good solubility of the prepared phthalonitriles in
organic solvents (in particular, in chloroform) allowed
1
their characterization by means of H NMR spectro-
scopy. The registered spectra contained the signals of
all protons of the structures corresponding to the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 12 2015

2780
TIKHOMIROVA et al.
(a)
D
(a)
D
λ, nm
λ, nm
D
(b)
(b)
D
λ, nm
λ, nm
Fig. 2. Electron absorption spectra of ethanol solutions of
initial compound (a) 3d and (b) compound 3d treated with
tin(II) chloride.
Fig. 1. Electron absorption spectra of solution of com-
pounds (a) 3а and (b) 3е in (1) DMF and (2) chloroform.
expected products. For example, the spectrum of
compound 3d (the numbering of the protons is shown
in the scheme) contained a triplet at 1.03 ppm (protons
of the terminal methyl group), a multiplet at 1.58 ppm
(the H8 protons of the γ-methylene group), a multiplet
at 1.85 ppm (the H7 protons of the β-methylene group),
a triplet at 4.11 ppm (the H6 protons of the α-me-
thylene group), a doublet at 7.06 ppm (the H5 protons
of the benzene ring in the ortho-position with respect
to the alkoxy group), a multiplet at 7.98 ppm (the H4
protons in the ortho-position with respect to the azo
group), a multiplet at 7.96 ppm (the H2 proton of the
phthalonitrile fragment), and a multiplet at 8.19–
8.28 ppm (the H1 and H3 protons of the phthalonitrile
fragment).
maximum at 378–491 nm assigned to the electronic
transitions in the azo dye chromophore system. The
band position was affected both by the compound
structure and the solvent nature. In particular, the
absorption band maximum of the nitrile 3a was found
at longer wavelength (the difference being up to
90 nm) in comparison with that of compounds 3b–3f
likely due to the strong electron-donor effect of the
NHC6H5 group, a part of the chromophore system of
compound 3а. The absorption band of the solutions in
chloroform of the nitriles containing the O-alkyl group
(3d–3f) was observed at higher wavelengths than that
of the solutions in DMF; in the cases of the nitriles 3a–
3c, the solvent effect was the opposite (Fig. 1).
The structure of the prepared nitriles was
additionally confirmed by their reduction with tin(II)
chloride in ethanol at room temperature. Azo dyes are
Electron absorption spectra of compounds 3a–f in
organic solvents contained a strong band with a
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SYNTHESIS AND PROPERTIES OF 4-[(Е)-(4'-R-PHENYL)DIAZENYL]PHTHALONITRILES
2781
Scheme 3.
N N
R
N
N
N N
R
N N
R
NC
NC
N
Co(OAc)2
N
Co
N
N
R
N N
3а−3f
N
N
N N
4а−е
R
NHC H (а), OH (b), OCOC H OC H (c), OC H (d), OC H15 (e), OCH2C6H5 (f).
R =
6
5
6
4
3
7
4
9
7
known to be split into a pair of the primary amines
under these conditions [11]; the distinct band in the
electron absorption spectrum of the solution simultane-
ously disappears. The similar behavior we observed,
for example, in the case of compound 3d (Fig. 2).
In particular, compound 4b was partially soluble in
aqueous alkali, and compounds 4c–4f containing acyl
or alkoxy moieties were insoluble in aqueous alkali but
soluble in chloroform and acetone.
The composition and structure of the prepared
phthalocyanines was confirmed by the data of
elemental analysis as well as IR and electron absorp-
tion spectroscopy. Thus, the IR spectra contained the
absorption bands typical of the phthalocyanines [14]
along with the bands corresponding to the functional
substituents of compounds 3a–3f.
The prepared precursors 3a–3f were further
transformed into the corresponding phthalocyanines
via the interaction with cobalt(II) acetate at 185–190°C
[1, 2] (Scheme 3).
The products were dark-violet (4a) or green (4b–4f)
powders. All prepared complexes were soluble in
DMF, whereas the solubility in other organic solvents
depended in the nature of the peripheral substituents.
Electron absorption spectra of solutions of
complexes 4a–f in organic solvents contained strong
Basic parameters of electron absorption spectra of phthalocyanines 4a–4f
λmax, nm (Drel)a
Compound
no.
chloroform
DMF
H2SO4 (conc.)
577 (1.00), 928 (0.91)
477 (1.00), 831 (0.66)
478 (0.88), 855 (1.00)
483 (1.00), 887 (0.83)
484 (1.00), 868 (0.70)
480 (1.00), 859 (0.69)
790
b
4а
4b
–
478 (1.00), 723 (0.48)
b
–
370 (1.00), 703 (0.63)
4c
365 (1.00), 642 (0.40), 709 (0.27)
360 (1.00), 650 (0.53), 707 (0.50)
357 (1.00),645 (0.47), 707 (0.51)
370 (1.00), 654 (0.50), 705 (0.47)
353 (1.00), 642 (0.49), 702 (0.57)
364 (1.00), 652 (0.45) 703 (0.72)
360 (1.00), 640 (0.40), 703 (0.93)
368 (1.00), 645 (0.47), 701 (0.90)
660
4d
4e
4f
b
СоРс
–
a Intensities of the absorption bands are referenced to the strongest one. b Insoluble.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 12 2015

2782
TIKHOMIROVA et al.
(a)
D
D
λ, nm
(b)
364
λ, nm
D
Fig. 3. Electron absorption spectra of compounds (1) 4a
and (2) 4c solutions in DMF.
absorption bands at 650–730 nm (π–π* electronic transi-
tions in the main conjugation path of the phthalo-
cyanine macrocycle) and 360–486 nm (electronic
transitions in the chromophore system of the azo dye)
(see the table and Fig. 3); similar features have been
earlier marked for the tetra-R-phenylazophenoxy-
phthalocyanines [8].
The azo chromophore nature strongly affected the
absorption bands position. For instance, the O-
alkylation resulted in a slight blue shift of the bands
(cf. the data for compounds 4b and 4d); the wave-
lengths of the absorption bands in the spectrum of the
complex containing the diphenylamine fragments (4a)
were increased as compared to those in the spectrum of
compound 4b, by 100 and 20 nm (for the short-wave
and long-wave bands, respectively) (see the table). The
observed features were due to the strong electron-
donor properties of the peripheral diphenylamine
substituents.
400
500
600
700
λ, nm
800
900
Fig. 4. Electron absorption spectra of compound 4d
solutions in (a) chloroform and (b) DMF (1) before and
(2) after the treatment with SnCl2.
associates stability. The decrease in the amount of the
π–π associates in the polar solvents like DMF results in
weakening of the short-wave absorption band [14].
Absorption bands of the solutions of all prepared
phthalocyanines in concentrated sulfuric acid were
observed at significantly longer wavelength as com-
pared to the solutions in the organic solvents (see the
table); that was due to the protonation of the nitrogen
meso-atoms of the phthalocyanine macrocycle [15].
The shift of the bands position observed in this work
was somewhat higher than that in the case of the non-
substituted cobalt phthalocyanine, due likely to the
protonation of the peripheral nitrogen atoms involved
in the conjugation with the macrocycle. The most
prominent red shift was observed in the case of
The ratio of intensities of the main Q band and that
at the range of vibrational satellite in the spectra of
complexes 4 depended on the solvent nature: in the
case of the solutions in chloroform the Q band was
relatively stronger than in the case of the solutions in
DMF (see the table). That was due likely to the change
in the association behavior of the phthalocyanine
molecules as a function of the solvent polarity. The
low dielectric constant of non-polar and low-polar
solvents weakens the solvent shielding of the inter-
molecular Pc–Pc interactions, thus enhancing the
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SYNTHESIS AND PROPERTIES OF 4-[(Е)-(4'-R-PHENYL)DIAZENYL]PHTHALONITRILES
2783
compound 4a containing peripheral fragments of the
Physicochemical parameters of the prepared
arylamine along with the azo groups.
compounds were studied using the equipment installed
at the Center for Joint Usage, Ivanovo State University
of Chemistry and Technology.
Regardless of the solvent nature the absorption
bands of the phthalocyanines prepared in this work
were observed at longer wavelengths as compared to
the earlier studied tetra-4-R-azophenoxyphthalocyani-
nes [8]. That was ascribed to the conjugation of the azo
dye with the macrocycle existing in compounds 4a–4f,
in contrast to the compounds containing the azo
chromophore separated from the phthalocyanine ligand
with a spacer (oxygen atom) [8].
4-[(E)-(4'-Anilinophenyl)diazenyl]phthalonitrile
(3a). Diazotization of 0.6 g (0.0042 mol) of 4-
aminophthalonitrile was performed as described in [9].
The so formed solution was added to a cooled solution
of 0.71 g (0.0042 mol) of diphenylamine in 5 mL of
DMF at vigorous stirring, maintaining the temperature
of the mixture below 10–15°C. The reaction com-
pletion was monitored using a flow-out test with diso-
dium 3-hydroxy-4-niroso-2,7-naphthalenedisulfonate
(weakly acidic medium). The reaction mixture was
diluted with 20 mL of water and 30 mL of ethyl
acetate. The organic layer was separated using a
separatory funnel, the solvent was distilled off, and the
target product was extracted with chloroform and
purified by column chromatography (М60 silica gel,
chloroform as eluent). Yield 0.95 g (70 %), mp 166°С.
IR spectrum (KBr), ν, cm–1: 3414 br (NH), 2231 s
Structures of the prepared cobalt phthalocyanines
4a–4d were additionally confirmed by their reduction
with tin(II) chloride in a chloroform–ethanol mixture
at room temperature. The initially green mixture turned
blue in the course of the process owing to the forma-
tion of the suspended reaction product insoluble in
chloroform.
Let us consider the changes of the reaction mixture
spectra after the reduction taking compound 4d as an
example (Fig. 4). The visible-range absorption was
almost absent due to the product insolubility in
chloroform. The absorption band found in the substrate
spectrum at 364 nm (DMF) disappeared after the
reduction, and the Q band suffered the red shift; those
changes pointed at decomposition of the peripheral azo
chromophores of the 4d complex.
1
(C≡N), 1614 s (NH), 1586 s (N=N), 1387 s (С–N). Н
NMR spectrum (CDCl3), δ, ppm: 8.27 s (1Н, Н1), 8.16
m (1Н, Н3), 7.93 m (2Н, Н4), 7.78 m (1Н, Н2), 7.42 m
(2Н, Н5), 7.23 m (2Н, Н7), 7.12 m (3Н, Н6,8), 6.30 s
(1Н, NН). Electron absorption spectrum, λmax, nm: 466
(chloroform); 491 (DMF). Found, %: C 73.45; H 4.01;
N 19.76. С20Н13N5. Calculated, %: С 74.29; Н 4.05; N
21.66.
To conclude, we prepared a series of earlier
unknown 4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles
and the corresponding cobalt phthalocyanines. Com-
parative analysis of the electron absorption spectra of
the prepared compounds revealed the influence of the
peripheral substituents and the solvent nature on the
chromophore properties.
4-[(E)-(4'-Hydroxyphanyl)diazenyl]phthalonitrile
(3b). Diazotization of 0.6 g (0.0042 mol) of 4-amino-
phthalonitrile was performed as described in [9]. The
so formed solution was added dropwise to a cooled
solution of 1.2 g (0.0042 mol) of 4-hydroxybenzoic
acid in 25 mL of 20 wt % aqueous solution of Na2CO3
at vigorous stirring, maintaining the temperature of the
mixture below 8–10°C. The reaction completion was
monitored using a flow-out test with disodium 3-hyd-
roxy-4-niroso-2,7-naphthalenedisulfonate (neutral
medium). The formed precipitate was filtered off,
washed with water, and dried. The product was
extracted with chloroform and purified by column
chromatography (М60 silica gel, chloroform as
eluent). Yield 1.8 g (86.5%), mp 190°С. IR spectrum
(KBr), ν, cm–1: 3500 br (OH), 2241 s (C≡N), 1581 s
EXPERIMENTAL
Electron absorption spectra of the solutions in
DMF, chloroform, and concentrated sulfuric acid
(325–900 nm) were recorded using a HITACHI U-2001
spectrophotometer at room temperature. IR spectra
(from thin films of the solution in chloroform or KBr
pellets; 400–4000 cm–1) were recorded using an Avatar
360 FT-IR ESP spectrometer. 1Н NMR spectra (5 wt %
solutions in CDCl3, TMS as reference) were recorded
using a Bruker DRX-500 spectrometer. Elemental
analysis was performed using a CHNS-O FlashEA
1112 series elemental analyzer.
1
(N=N), 1328 s (ОH). Н NMR spectrum (CDCl3), δ,
ppm: 8.75 s (1Н, OН), 8.29 s (1Н, Н1), 8.19 m (1Н,
Н3), 7.96 m (1Н, Н2), 7.03 m (2Н, Н4), 7.01 m (2Н,
Н5). Electronic absorption spectrum, λmax, nm: 382
(chloroform); 385 (DMF). Found, %: C 66.93; H 4.00;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 12 2015

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TIKHOMIROVA et al.
N 21.98. С14Н8N4O. Calculated, %: С 67.74; Н 3.25; N
22.57.
4-[(E)-(4'-Heptyloxyphenyl)diazenyl]phthalo-
nitrile (3e). Yield 0.4 g (57%), mp 131°С. IR spec-
trum (KBr), ν, cm–1: 2923 s, 2854 (СН), 2230 s (C≡N),
4-{4'-[(E)-(4"-Propoxybenzoyl)oxyphenyl]diazenyl}-
phthalonitrile (3c). A mixture of 0.3 g (0.002 mol) of
4-(4'-propoxy)benzoic acid and 0.6 mL (0.005 mol) of
thionyl chloride was heated at 40–50°С at stirring till
the gas evolution ceased (about 2 h). 0.9 g (0.0036 mol)
of compound 3b and 1 mL of pyridine were then
added, and the reaction mixture was refluxed at 85°С
during 2 h. The obtained mass was poured into water;
the precipitate was filtered off, washed with water till
neutral reaction of the washings, and dried. The
product was extracted with chloroform and purified by
column chromatography (М60 silica gel, chloroform
as eluent). Yield 0.7 g (47%), mp 148°С. IR spectrum
(KBr), ν, cm–1: 2924 s, 2852 (СН), 2235 s (C≡N),
1
1598 s (N=N), 1253 s (С–O–С). Н NMR spectrum
(CDCl3), δ, ppm: 8.28 s (1Н, Н1), 8.19 m (1Н, Н3),
7.95 m (1Н, Н2), 7.49 m (2Н, Н4), 7.27 m (2Н, Н5),
4.10 m (2Н, Н6), 1.86 m (2Н, Н7), 1.66 m (2Н, Н8),
1.27 m (4Н, Н9,10), 0.92 m (5Н, Н11,12). Electronic
absorption spectrum, λmax, nm: 382 (chloroform); 380
(DMF). Found, %: C 70.10; H 5.41; N 17.73.
С21Н22N4O. Calculated, %: С 72.81; Н 6.40; N 16.17.
4-[(E)-(4'-Benzyloxyphenyl)diazenyl]phthalo-
nitrile (3f). Yield 0.6 g (86%), mp 152°С. IR spectrum
(KBr), ν, cm–1: 2914 m (СН2), 2228 s (C≡N), 1595 s
1
(N=N), 1250 s (С–O–С). Н NMR spectrum (CDCl3),
δ, ppm: 8.28 s (1Н, Н1), 8.19 m (1Н, Н3), 7.95 m (1Н,
Н2), 7.45 m (2Н, Н4), 7.28 m (5Н, Н7,8,9), 7.14 s (2Н,
H5), 5.21 s (2Н, CН2). Electronic absorption spectrum,
1
1729 s (С=О), 1267 s (Ar–O–Alk), 1608 s (N=N). Н
NMR spectrum (CDCl3), δ, ppm: 8.28 s (1Н, Н1), 8.19
m (1Н, Н3), 7.97 m (2Н, Н4), 7.95 m (1Н, Н2), 7.49 m
(2Н, Н5), 7.03 m (2Н, Н7), 6.22 m (2Н, Н8), 1.61 m
(2Н, Н9), 0.90 m (3Н, Н10). Electronic absorption spec-
trum, λmax, nm: 380 (chloroform); 387 (DMF). Found,
%: C 69.93; H 4.12; N 13.18. С24Н18N4O3. Calculated,
%: С 70.23; Н 4.42; N 13.65.
λ
max, nm: 382 (chloroform); 379 (DMF). Found, %: C
74.54; H 4.17; N 16.56. С21Н14N4O. Calculated, %: С
74.54; Н 4.17; N 16.56.
Cobalt(II) tetra-4-[(E)-(4'-R-phenyl)diazenyl]-
phthalocyanines (4a–4f). A mixture of 0.001 mol of
the corresponding phthalonitrile 3a–3f and 0.19 g
(0.0003 mol) of cobalt(II) acetate was thoroughly
ground, heated up to 185–190°С in a quartz ampule,
and kept at this temperature till solidification of the
reaction mass. The latter was then cooled down to
ambient, ground, washed with 5 wt% aqueous
hydrochloric acid till colorless washings and then with
water till neutral reaction of the washings. The
obtained solid substance was dried, extracted with
DMF (4a, 4b) or with a 5 : 1 chloroform–ethanol
mixture (4c–4f), and purified by column chromato-
graphy [М60 silica gel; eluent: DMF (4a, 4b) or a 5 : 1
chloroform–ethanol mixture (4c–4f)].
4-[(E)-(4'-Alkoxyphenyl)diazenyl]phthalonitriles
(3d–3f). A mixture of 30 mL of DMF, 0.5 g (0.002 mol)
of compound 3b, 0.375 g (0.0027 mol) of potassium
carbonate, and 0.0019 mol of the corresponding alkyl
bromide was heated on a boiling water bath during 2 h
at stirring and then poured into 300 mL of water. In the
cases of compounds 3d and 3e the formed oily layer
was separated using a separatory funnel and extracted
with acetone; the solvent was then distilled off. In the
case of compound 3f, the precipitate formed after
pouring into water was separated, washed with water,
and dried. The product was extracted with chloroform
and purified by column chromatography (М60 silica
gel, chloroform as eluent).
Cobalt(II) tetra-4-[(E)-(4'-anilinophenyl)diazenyl]-
phthalocyanine (4a). Yield 0.12 g (36%). IR spectrum
(KBr), ν, cm–1: 3409 br (NН), 1592 s (N=N). Found,
%: C 69.86; H 4.02; N 20.02. С80Н52CoN20. Cal-
culated, %: C 71.05; H 3.88; N 20.71.
4-[(E)-(4'-Butoxyphenyl)diazenyl]phthalonitrile
(3d). Yield 0.45 g (74%), mp 105°С. IR spectrum
(KBr), ν, cm–1: 2937 s, 2852 (СН), 2233 s (C≡N),
1
1601 s (N=N), 1257 s (С–O–С). Н NMR spectrum
Cobalt(II) tetra-4-[(E)-(4'-hydroxyphenyl)diazenyl]-
phthalocyanine (4b). Yield 0.16 g (60.84%). IR
spectrum (KBr), ν, cm–1: 3400 br (OH), 1591 s (N=N),
1330 s (ОH). Found, %: C 63.02; H 3.42; N 20.93.
С56Н32CoN16О4. Calculated, %: C 63.94; H 3.07; N 21.30.
(CDCl3), δ, ppm: 8.28 m (1Н, Н1), 8.19 m (1Н, Н3),
7.98 m (2Н, Н4), 7.96 m (1Н, Н2), 7.06 m (2Н, Н5),
4.11 m (2Н, Н6), 1.85 m (2Н, Н7), 1.58 m (2Н, Н8),
1.03 m (3Н, Н9). Electronic absorption spectrum, λmax
,
nm: 383 (chloroform); 378 (DMF). Found, %: C
70.63; H 4.92; N 18.18. С18Н16N4O. Calculated, %: С
71.04; Н 5.30; N 18.41.
Cobalt(II) tetra-4-{4'-[(E)-(4''-propoxybenzoyl)
oxyphenyl]diazenyl}phthalocyanine (4c). Yield
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 12 2015

SYNTHESIS AND PROPERTIES OF 4-[(Е)-(4'-R-PHENYL)DIAZENYL]PHTHALONITRILES
2785
0.29 g (68%). IR spectrum (KBr), ν, cm–1: 2925 s,
2850 (СН), 1731 s (С=О), 1257 s (Ar–O–Alk), 1600 s
(N=N). Found, %: C 67.61; H 4.55; N 13.03.
С84Н88CoN16О4. Calculated, %: C 67.80; H 4.27; N 13.18.
3. Atsay, A., Özceşmeci, I., Okur, A.I., and Gül, A.,
J. Porphyrins Phthalocyanines, 2008, vol. 12, nos. 3–6,
p. 451. DOI: 10.1134/ 2FS1070363213.
4. Airtaş, M.S., Çelebi, M., Gümüş, S., Özdemir, S., and
Okumuş, V., Dyes and Pigments, 2013, vol. 99, no. 2,
p. 423. DOI: 10.1016/j.dyepig.2013.05.019.
5. Selivanova, G.A., Amosov, E.V., Vasil’ev, V.G.,
Luk’yanets, E.A., and Shteingarts, V.D., RF Patent
2479573, 2013, Byull. Izobret., 2013, no. 11.
6. Tikhomirova, T.V., Badaukaite, R.A., Kulinich, V.P.,
and Shaposhnikov, G.P., Russ. J. Gen. Chem., 2011,
vol. 81, no. 11, p. 2355. DOI: 10.1134/
S1070363211110235.
7. Tikhomirova, T.V., Badaukaite, R.A., Kulinich, V.P.,
Shaposhnikov, G.P., Zharnikova, N.V., Anan’eva, G.A.,
Bykova, V.V., and Usol’tseva, N.V., Zhid. Krist. Prakt.
Ispol’zovanie, 2011, no. 3 (37), p. 15.
8. Tikhomirova, T.V., Badaukaite, R.A., Kulinich, V.P.,
and Shaposhnikov, G.P., Russ. J. Gen. Chem., 2013,
vol. 83, no. 1, p. 116. DOI: 10.1134/
S1070363213010209.
9. Nosova, G.I., Yakimanskii, A.V., Kudryavtsev, V.V.,
Abramov, I.G., Lyskov, V.B., Makovkina, O.V., and
Gorban’, N.B., RF Patent 2 369 597(13), 2009, Byull.
Izobret., 2009, no. 28.
Cobalt(II) tetra-4-[(E)-(4'-butoxyphenyl)diazenyl]-
phthalocyanine (4d). Yield 0.20 g (63.5%). IR spec-
trum (KBr), ν, cm–1: 2924 s, 2859 s (СН), 1598 s
(N=N), 1250 s (С–O–С). Found, %: C 67.36; H 5.12;
N 17.36. С72Н64CoN16О4. Calculated, %: C 67.76; H
5.05; N 17.56.
Cobalt(II) tetra-4-[(E)-(4'-heptyloxyphenyl)di-
azenyl]phthalocyanine (4e). Yield 0.23 g (64%). IR
spectrum (KBr), ν, cm–1: 2922 s, 2852 (СН), 1597 s
(N=N), 1252 s (С–O–С). Found, %: C 69.79; H 6.59;
N 15.43. С84Н88CoN16О4. Calculated, %: C 69.84; H
6.14; N 15.51.
Cobalt(II) tetra-4-[(E)-(4'-benzyloxyphenyl)di-
azenyl]phthalocyanine (4f). Yield 0.22 g (62%). IR
spectrum (KBr), ν, cm–1: 2922 s (СН), 1601 s (N=N),
1249 s (С–O–С). Found, %: C 69.99; H 4.30; N 15.50.
С84Н56CoN16О4. Calculated, %: C 71.43; H 4.00; N
15.87.
10. Stepanov, B.I., Vvedenie v khimiyu i tekhnologiyu
organicheskikh krasitelei (Introduction to the Chemistry
and Technology of Organic Dyes), Moscow: Khimiya,
1984.
11. Lisitsyn, V.N., Khimiya i tekhnologiya promezhu-
tochnykh produktov (Chemistry and Technology of
Intermediate Products), Moscow: Khimiya, 1987.
12. Dayer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, New York: Enclewood Cliffs,
1970.
ACKNOWLEDGMENTS
This work was performed in the frame of the
governmental contract of the Ministry of Education
and Science of Russia and financially supported by the
Russian Scientific Foundation (agreement no. 14-23-
00204).
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i
ihk strukturnye
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 12 2015