Synthesis and properties of phthalonitriles with an azo chromophore and related phthalocyanines

Article abstract of DOI:10.1134/S1070363213010209

The 4-R-phenylazophenoxyphthalonitriles were synthesized by the reaction of 4-bromophthalonitrile with 4-R-phenylazophenols and were used to obtain tetra-R-phenylazophenoxyphthalocyanines and their metal complexes. The effect of substituents on the spectr

Full text of DOI:10.1134/S1070363213010209

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 1, pp. 116–123. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © T.V. Tikhomirova, R.A. Badaukaite, V.P. Kulinich, G.P. Shaposhnikov, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 1, pp. 124–131.
Synthesis and Properties of Phthalonitriles
with an Azo Chromophore and Related Phthalocyanines
T. V. Tikhomirova, R. A. Badaukaite, V. P. Kulinich, and G. P. Shaposhnikov
Research Institute of Macroheterocycles, Ivanovo State University of Chemical Technology,
pr. Engelsa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
Received November 22, 2011
Abstract—The 4-R-phenylazophenoxyphthalonitriles were synthesized by the reaction of 4-bromo-
phthalonitrile with 4-R-phenylazophenols and were used to obtain tetra-R-phenylazophenoxyphthalocyanines
and their metal complexes. The effect of substituents on the spectral and other properties of the synthesized
compounds was established.
DOI: 10.1134/S1070363213010209
The synthesis and properties of substituted phthalo-
cyanines are described in literature in detail [1, 2]. One
of the drawbacks of the majority of these compounds
is a narrow color range, so the work aimed at ex-
tending the range of absorption of phthalocyanines is
important and relevant. One of the directions in
solving this problem is the introduction into the
phthalocyanine molecule of a substituent with its
proper chromophore system [3–5].
In continuation of our research in this direction [4,
5] we report here on the synthesis of nitriles VII and
phthalocyanines VIII–XI based on them containing
azo chromophores on the molecule periphery.
NaO
COONa
NaNO2,
2HCl
N
N
ONa
III
R1
R
NH2
R
N
+NCl_
R1
Ia_Ic
R1
IIa_IIc
R
IVa_IVc
HCl
NC
NC
Br
, K2CO3, DMF
N
R
N
OH
R1
NC
NC
O
Хр
VI
Va_Vc
VIIa_VIIc
Хр = O
N
N
R
R1
R = CH3, R1 = H (a); R = CH3, R1 = CH3 (b); R = NHCOCH3; R1 = H (c).
116

SYNTHESIS AND PROPERTIES OF PHTHALONITRILES
117
Synthesis of nitriles VIIa–VIIc was carried out in
accordance with the scheme above.
Tramsmission, %
Diazotization of the substituted anilines Ia–Ic
afforded diazo compounds IIa–IIc, which undergo the
azo coupling with sodium p-hydroxybenzoate III. This
reaction belongs to particular cases of the azo coupling
and it proceeds with the replacement of a substituent
(carboxyl group) [6]. By adding concentrated
hydrochloric acid to a solution of a compound IVa–
IVc respective dyes Va–Vc as a R-substituted phenyl-
azophenols were isolated.
The nucleophilic substitution of the bromine atom
in 4-bromophthalonitrile VI synthesized by the known
method [7] by the appropriate azo dye residue
(CHROM) in the DMF medium in the presence of
K2CO3 afforded the corresponding new R-substituted
phenylazophenoxyphthalonitriles VIIa–VIIc.
The choice of 4-bromophthalonitrile VI as a
substrate for nucleophilic substitution reactions is
defined by the fact that the electron-withdrawing
substituent (C≡N group) in the benzene ring causes
polarization of the C–Br bond and the appearance of
effective positive charge on the carbon atom bearing
the bromine, which contributes to the easy replacement
of the latter [8]. The role of potassium carbonate
consists in the transformation of the CHROM–OH in
bipolar ion with higher reactivity in the nucleophilic
substitution reactions [9]. The choice of DMF as a
solvent is due to the fact that in aprotic solvents
dissolving well the source nitrile VI the reaction rate
of nucleophilic substitution increases by 3–5 orders of
magnitude over that performed in non-polar solvents [10].
Wavenumber, cm–1
Fig. 1. IR spectrum of nitrile VIIc.
electron spectroscopy. Chromatograms of the phthalo-
nitriles VIIa and VIIb contained single peaks indicat-
ing the absence of impurities. Mass spectra of nitriles
VIIa, VIIb have the signals corresponding to the main
molecular ion (m/z 338 and 352 in the mass spectra of
VIIa and VIIb, respectively). Among the registered
peaks of the products of their fragmentation, the
principal are of m/z 247 and 219, corresponding to the
4-azophenoxyphthalonitrile and the residue of
phenoxyphthalonitrile, respectively.
Comparing the IR spectra of the source and target
phthalonitriles, the preservation should be noted of the
bands at 2230–2232 cm–1 corresponding to the stretch-
ing vibrations of the cyano group. In the spectra of
each compound an absorption band appears in the
range 1247–1250 cm–1 characteristic of the Ar–O–Ar
vibrations. In the region of 2919–2930 cm–1 a band is
observed corresponding to the stretching vibrations of
CH bonds of methyl groups, and at 1592–1585 cm–1, a
band corresponding to stretching vibrations of the azo
group (N=N). In the spectrum of nitrile VIIc there is
an additional absorption band at 1671 cm–1 corres-
ponding to the C=O of the amide group and at 3307 cm–1,
characteristic of the secondary amine groups (Fig. 1) [11].
Synthesized phthalonitriles VIIa–VIIc are powders
of red-orange color, readily soluble in organic solvents
(acetone, DMF, ethanol).
It is noted that the nature and the amount of the
substituents R and R1 in the phthalonitrile molecule
affect the melting point of the substance. While the
melting onset temperature of 4-[4'-(4"-methyl-
phenylazo)phenoxy]phthalonitrile VIIa is 140°C, the
introduction of an additional methyl group R1 leads to
a significant decrease in the melting temperature: 4-[4'-
(2',4"-dimethylphenylazo)phenoxy]phthalonitrile VIIb
melts at 43°C. Replacing the methyl group R by
acylamino group also reduces the melting temperature
to 108°C.
The good solubility of the synthesized phthalo-
nitriles in organic solvents, particularly in chloroform,
allowed us their study by 1H NMR spectroscopy.
9
4
8
5
1
NC
NC
O
N
N
CH3
The identification of the compounds VIIa–VIIc
was performed using data of elemental analysis, gas
chromatography–mass spectrometry, IR, 1H NMR, and
6
7
11
10
2
3
VIIa
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

118
TIKHOMIROVA et al.
Thus, considering the 1H NMR spectrum of
located in the ortho position to the azo group of the
phenoxy residue.
compound VIIa, we note the following signals. A
triplet at 2.48 ppm corresponds to the resonance of the
three protons of the CH3 groups. In a weak field there
are two multiplets at 7.24–7.38 ppm corresponding to
four protons (8–11) of benzene ring of the p-toluidine
residue and two protons (4, 6) of the benzene ring in
the ortho position to the oxygen atom of the phenoxy
residue. The signals of three protons (1–3) of phthalo-
nitrile are also the multiplets in a weak field at 7.78–
7.88 ppm, and the most downfield is a multiplet at
8.3 ppm corresponding to the signals of protons (5, 7),
By heating the synthesized phthalonitriles VIIa–
VIIc with potassium carbonate playing the role of an
alkaline agent [9] at 185–190°C and subsequent
reprecipitation of the products obtained from con-
centrated sulfuric acid we isolated the corresponding
tetra-R-phenylazophenoxyphthalocyanines
VIIIa–
VIIIc. The synthesis of metallocomplexes IX–XI was
performed by reacting the phthalonitriles VIIa–VIIc
with anhydrous cobalt, copper, and nickel chlorides at
185–190°C.
OXp
XpO
N
NC
NC
OXp
N
N
N
N
N
M
N
VII
N
XpO
M = 2H (VIII), Co (IX), Cu (X), Ni (XI); R = CH3, R1 = H (a); R = CH3, R1 = CH3 (b); R = NHCOCH3; R1 = H (c).
OXp
MPc(OXp)4
The phthalocyanines obtained were purified by
reprecipitation from concentrated sulfuric acid followed
by washing with organic solvents in a Soxhlet
apparatus and finally by the column chromatography
on silica gel M 60.
Phthalocyanines VIII–XI are green and blue-green
powders. Their solubility in organic solvents depends
on the nature and quantity of the substituents R and R1.
All compounds are soluble in DMF, the presence of
methyl groups in the macromolecules VIIIa, VIIIb–
XIa, XIb makes them soluble in chloroform, the
compounds with acylamino groups VIIIc–XIc are
soluble in acetone.
Identification of the obtained phthalocyanines was
carried out using the data of elemental analysis, IR and
electronic spectroscopy. In the IR spectra of the
synthesized compounds VIII–XI the absorption band
typical of the aryloxy-, methoxy- and azo-groups of
the corresponding phthalonitriles were retained. In
addition, in the IR spectra of substituted H2Pc the
presence of absorption bands at 1008 cm–1 was noted
characteristic of metal-free phthalocyanines [12].
The electron absorption spectra (EAS) of the
synthesized phthalocyanines in organic solvents and
sulfuric acid are presented in the table and Figs. 2–5.
Spectral curves of tetra-R-phenylazophenoxyphthalo-
cyanines VIIIa–VIIIc in organic solvents are
characterized by a doublet in the long-wavelength
region (Fig. 2, table), which is typical of the metal-free
compounds and is due to the decrease in the molecular
symmetry from D4h to D2h [13] . A distinctive feature
of all spectra is the presence of a strong absorption
band in the region of 341–367 nm originating from
electronic transitions in the chromophore system of the
azo dyes attached to the benzene rings of the
phthalocyanine ligand (Fig. 2, table). In going from
phthalocyanines VIIIa–VIIIc to their metallocom-
plexes IX–XI their symmetry increases from D2h to
D4h, resulting in merging of two components of Q-
band into one [13], which is undergoes a red shift in
comparison with the Q-band of the corresponding
unsubstituted MPc (table, Fig. 3). The azo-chromo-
phore nature virtually does not affect the position of
the long-wavelength band in the EAS (Fig. 3, table).
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SYNTHESIS AND PROPERTIES OF PHTHALONITRILES
119
The position of the absorption bands in the EAS of the synthesized phthalocyanines
λmax, nm (D/Dmax
DMF
)
Comp.
no.
М
R, R1
chloroform
acetone
–
Conc. H2SO4
2H
R = CH3,
R1 = H
345 (1.00), 702 (0.71), 349 (1.00), 698 (0.67),
666 (0.63), 641 (0.31), 670 (0.60), 641 (0.40),
468 (1.00), 891
(0.55), 836 (0.54)
VIIIа
VIIIb
VIIIc
607 (0.21)
610 (0.29)
2H
2H
R = CH3,
R1 = CH3
350 (1.00), 700 (0.92), 359 (1.00), 697 (0.76),
665 (0.82), 640 (0.34), 669 (0.72), 637 (0.41),
–
475 (1.00), 901
(0.60), 841 (0.57),
605 (0.29)
605 (0.28)
R = CH3,
–
366 (1.00), 700 (0.62), 367 (1.00), 699 (0.66)
669 (0.60), 635 (0.41), 667 (0.64), 639 (0.32), (0.76), 817 (0.66),
610 (0.29)
341 (1.00), 674 (0.66), 345 (1.00), 666 (0.59),
613 (0.35) 603 (0.22)
470 (1.00), 873
R1 = NHCOCH3
610 (0.22)
767 (0.48)
Co
Co
Co
Cu
Cu
Cu
Ni
R = CH3,
R1 = H
–
472 (1.00), 818
(0.58)
IXа
IXb
IXc
Xа
R = CH3,
R1 = CH3
345 (1.00), 675 (0.65), 345 (1.00), 670 (0.65),
–
479 (1.00), 824
(0.44)
610 (0.29)
605 (0.21)
R = CH3,
–
365 (1.00), 667 (0.79), 365 (1.00), 665 (0.89),
472 (1.00), 802
(0.75), 710 (0.43)
R1 = NHCOCH3
605 (0.24)
600 (0.22)
R = CH3,
R1 = H
345 (1.00), 680 (0.65), 345 (1.00), 675 (0.55),
605 (0.25) 610 (0.21)
–
470 (1.00), 839
(0.82), 740 (0.35)
R = CH3,
R1 = CH3
344 (1.00), 681 (0.99), 355 (1.00), 675.5 (0.71),
–
–
–
–
–
476 (1.00), 846
(0.88), 740 (0.39)
Xb
615 (0.31)
610 (0.52)
R = CH3,
–
365 (1.00), 675 (0.71),
610 (0.26)
470 (1.00), 824
(0.72), 725 (0.20)
Xc
R1 = NHCOCH3
R = CH3,
R1 = H
351 (1.00), 671 (0.81), 341 (1.00), 672 (0.62),
616 (0.26) 616 (0.47)
470 (1.00), 814
(0.78), 722 (0.26)
XIа
XIb
XIc
Ni
R = CH3,
R1 = CH3
340 (1.00), 675 (0.92), 363 (1.00), 673 (0.64),
480 (1.00), 821
(0.71), 727 (0.25)
610 (0.34)
605 (0.33)
Ni
R = CH3,
–
350 (1.00), 677 (0.70),
610 (0.31)
470 (1.00), 800
(0.84), 705 (0.32)
R1 = NHCOCH3
The nature of the absorption bands and the ratio of
their intensities in the spectra of the synthesized phthalo-
cyanines point to the tendency of the metallocom-
plexes to association in solution (Fig. 4, table). It is
important to note that the tendency to association of
the Co(II) complexes is considerably less expressed
than that of Cu(II) and Ni(II) complexes. This originates
from the higher coordinating ability of cobalt. Cobalt
D
D
λ, nm
Fig. 3. Electron absorption spectra in DMF: (1) IXb, (2)
IXc.
λ, nm
Fig. 2. Electron absorption spectrum of phthalocyanine
VIIIa in chloroform.
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120
TIKHOMIROVA et al.
(a)
D
D
λ, nm
λ, nm
Fig. 5. Electron absorption spectra in sulfuric acid: (1) Xb,
(2) Xa, (3) Xc.
(b)
D
spectra of all phthalocyanines save the nickel com-
plexes (see the table). Thus, depending on the nature of
the metal-chelating agent, in DMF a red shift is
observed of the absorption bands in the sequence:
Co → Ni → Cu. Replacing the solvent by chloroform
alters the picture: Ni → Co → Cu (see the table). The
replacement of organic solvents by concentrated
sulfuric acid is known to result in a significant red shift
of the absorption bands due to the protonation of the
phthalocyanine macroring at the nitrogen meso-atoms
[16], which occurs in the spectra of all synthesized
phthalocyanines. However, the shift in the case of the
compounds synthesized by us is somewhat smaller
than that of the unsubstituted phthalocyanines, and
increases in the following order: VIIIc–XIc < VIIIa–
XIa < VIIIb–XIb (Fig. 5, table). We believe that it
due to the participation of the peripheral nitrogen
atoms of acylamido and azo groups in the processes of
protonation and simultaneous decrease in the degree of
protonation of the meso-nitrogen atoms of the macroring.
λ, nm
Fig. 4. Electron absorption spectra of compounds (a) IXb
and (b) XIa: (1) in chloroform, (2) in DMF.
phthalocyanine in aprotic solvents form extra-com-
plexes with the solvent molecules as extraligands
preventing the intermolecular interactions [14].
The comparative analysis of the EAS of phthalo-
cyanines in DMF and chloroform (Fig. 4, table) shows
that the nature of the solvent, in particular, its polarity
also affects the propensity of the MPc molecules to the
associative processes. The low dielectric permeability
of nonpolar and low-polar solvents reduces the
screening effect of the Pc–Pc intermolecular
interaction by the solvent and, consequently,
contributes to the formation of associates and increases
their stability compared to solutions in polar solvent
(DMF) [15].
Our studies of the synthesized phthalocyanines,
which are well soluble in organic solvents, showed a
possibility of their application as fat-soluble dyes for
dyeing waxes, hydrocarbons, and plastics.
EXPERIMENTAL
The electron absorption spectra of the compounds
obtained were measured on a Hitachi U-2001
spectrophotometer, the IR spectra were recorded on a
spectrophotometer AVATAR 360 FT-IR in the 400–
1
Changing the solvent from DMF to chloroform
results in a red shift of the long-wavelength band in the
4000 cm–1 from thin films, the H NMR spectra were
taken on a Bruker AMD-200 instrument from solutions
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SYNTHESIS AND PROPERTIES OF PHTHALONITRILES
121
in CDCl3, the mass spectra were measured on a Varian
Saturn 2000K instrument. Elemental analysis was
performed on a FlashEA 1112 CHNS-O Analyzer.
VI, 2.07 g (0.015 mol) of potassium carbonate, and
0.015 mol the corresponding R-phenylazophenol Va–
Vc. The resulting mixture was heated while stirring to
140–145°C and kept at this temperature for 2 h. The
reaction mixture was poured with stirring into 300 ml
of water. The precipitate was filtered off, washed with
5% sodium hydroxide solution until the filtrate was
colorless, and then with water until the filtrate was
neutral. The resulting precipitate was dried in air. Final
purification was performed by column chromato-
graphy on alumina using chloroform as eluent.
Synthesis of monoazodyes (general procedure)
[6]. A porcelain beaker equipped with a stirrer and a
thermometer was charged at stirring with 100 ml of
water, 30 ml of concentrated hydrochloric acid
(0.27 mol), and 0.1 mol of the corresponding substituted
amine. The resulting solution was cooled to 0–3°C in
an ice-salt mixture. At this temperature was added at
stirring dropwise from a dropping funnel 24 ml of 30%
solution of sodium nitrite (0.13 mol). After completion
of the sodium nitrite addition the stirring continued at
2–3°C for 30 minutes. During the reaction an acidic
environment was maintained by adding dropwise
hydrochloric acid. The substituted phenyldiazonium
chloride thus obtained was immediately used in the
stage of azo coupling.
4-[4'-(4"-Methylphenylazo)phenoxy]phthalonitrile
(VIIa) was obtained along the general procedure using
3.18 g of 4-(4'-methylphenylazo)phenol. Yield 3.25 g
(64.20%), mp 140°C. IR spectrum (film): 2232 (C≡N),
1247 (Ar–O–Ar), 1586 (N=N), 2920 (CH3). Mass
1
spectrum (m/z): 338. H NMR spectrum (CDCl3), δ,
ppm: 8.03 m (2H, H5,7), 7.88 m (2H, H1,3), 7.78 s (2H,
H2), 7.38 m (2H, H8,10), 7.29 s (4H, H4,6), 7.24 m (4H,
H9,11), 2.48 m (CH3). Found, %: C 74.43, H 4.30, N
16.28. C21H14N4O. Calculated, %: C 74.54, H 4.17, N
16.56.
In a porcelain beaker equipped with a stirrer and a
thermometer was placed 32 ml of 25% sodium
carbonate solution (0.08 mol), 8.00 g (0.20 mol) of
sodium hydroxide, and 13.80 g (0.10 mol) of p-hyd-
roxybenzoic acid. The resulting solution was cooled to
8–10°C by adding ice. Then, at vigorous stirring was
added dropwise from a dropping funnel a substituted
phenyldiazonium chloride. The coupling was carried
out at a temperature of 14–15°C in alkaline medium.
After adding the total diazo component the stirring was
continued for another 30 min. The resulting precipitate
was filtered off on a Buechner funnel, washed with
15% hydrochloric acid and with water until neutral
reaction. The resulting product was dried in air. The
target compound was extracted in a Soxhlet apparatus
with ethyl alcohol, ethanol was distilled off, and the
dye was dried in air.
4-[4'-(2',4"-Dimethylphenylazo)phenoxy]phthalo-
nitrile (VIIb) was obtained along the general
procedure using 3.39 g of 4-(2',4'-dimethylphenylazo)
phenol. Yield 3.76 g (71.30%), mp 43°C. IR spectrum
(film): 2231 (C≡N), 1249 (Ar–O–Ar), 1586 (N=N),
2919 (CH3). Mass spectrum (m/z): 352. Found, %: C
74.63, H 4.93, N 15.43. C22H16N4O. Calculated, %: C
74.98, H 4.58, N 15.90.
4-[4'-(4"-Acetamidophenylazo)phenoxy]phthalo-
nitrile (VIIc) was obtained along the general proce-
dure using 4.15 g of 4-(4'-acetamidophenylazo)phenol.
Yield 3.91 g (68.50%), mp 108°C. IR spectrum (film):
2230 (C≡N), 1249 (Ar–O–Ar), 1592 (N=N), 2929
(CH3), 1671 (C=O), 3307 (N–H sec.). Found, %: C
68.96, H 4.74, N 18.87. C22H15N5O2. Calculated, %: C
69.28, H 3.96, N 18.36.
4-(4'-Methylphenylazo)phenol (Va) was obtained
along the general procedure, using 10.70 g of p-tolu-
idine. Yield 14.27 g (67.3%).
4-(2',4'-dimethylphenylazo)phenol (Vb) was ob-
tained along the general procedure, using 12.4 ml of
m-xylidine. Yield 17.08 g (75.60%).
Synthesis of tetra-R-phenylazophenoxyphthalo-
cyanines (general procedure). Thoroughly ground
mixture of 0.001 mol of the corresponding R-phenyl-
azophenoxyphthalonitrile VIIa–VIIc and 0.21 g
(0.0015 mol) of potassium carbonate was placed in a
glass tube, heated to 185–195°C, and maintained at
this temperature for 1 h. After cooling, the reaction
mixture was ground and dissolved in concentrated
sulfuric acid. The resulting solution was poured on ice.
The precipitate was filtered off on a glass frit filter and
washed with water until neutral reaction. Then the
4-(4'-Acetamidophenylazo)phenol (Vc) was ob-
tained along the general procedure, using 15.00 g of p-
aminoacetanilide. Yield 9.11 g (67.13%).
Synthesis of R-phenylazophthalonitriles (general
procedure). A flask fitted with a stirrer, reflux
condenser, and thermometer was charged with 30 ml
of DMF, 2.07 g (0.01 mol) of 4-bromophthalonitrile
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

122
TIKHOMIROVA et al.
obtained powder was washed with acetone in a Soxhlet
apparatus, and the final purification was performed by
column chromatography on silica gel M 60, using as
eluent chloroform (VIIIa, VIIIb) or DMF (VIIIc).
Tetra-{4-[4'-(4"-methylphenylazo)phenoxy]}-
phthalocyanine (VIIIa) was obtained along the
general procedure using 0.34 g of 4-[4-(4'-methylp-
henylazo)phenoxy]phthalonitrile. Yield 2.51 g (46.26%).
Found, %: C 73.93, H 5.20, N 16.28. C84H58N16O4.
Calculated, %: C 74.43, H 4.31, N 16.53. EAS in
chloroform, λmax, nm: 345, 607, 641, 666, 702; in
DMF, λmax, nm: 349, 610, 641, 670, 698; in
concentrated sulfuric acid, λmax, nm: 468, 836, 891.
Tetra-4-[4'-(2',4"-dimethylphenylazo)phenoxy]-
phthalocyanine (VIIIb) was obtained along the
general procedure using 0.35 g of 4-[4'-(2',4"-dimethyl-
phenylazo)phenoxy]phthalonitrile. Yield 2.54 g (44.95%).
Found, %: C 74.54, H 4.93, N 16.29. C88H66N16O4. Cal-
culated, %: C 74.88, H 4.71, N 15.88. EAS in chloro-
general procedure using 0.34 g of 4-[4-(4'-methyl-
phenylazo)phenoxy]phthalonitrile and 0.19 g of cobalt
chloride. Yield 1.95 g (34.60%). Found, %: C 71.19, H
4.20, N 15.68. C84H56CoN16O4. Calculated, %: C
71.43, H 4.00, N 15.87. EAS in chloroform, λmax, nm:
341, 613, 674; in DMF, λmax, nm: 345, 603, 666; in
concentrated sulfuric acid, λmax, nm: 472, 818.
Tetra-4-[4'-(2',4"-dimethylphenylazo)phenoxy]-
phthalocyanine cobalt (IXb) was obtained along the
general procedure using 0.35 g of 4-[4'-(2',4'-di-
methylphenylazo)phenoxy]phthalonitrile and 0.19 g of
cobalt chloride. Yield 2.06 g (32.56%). Found, %: C
71.14, H 4.13, N 15.29. C88H64CoN16O4. Calculated,
%: C 71.98, H 4.39, N 15.26. EAS in chloroform, λmax
,
nm: 345, 610, 675; in DMF, λmax, nm: 345, 605, 670,
in concentrated sulfuric acid, λmax, nm: 479, 824.
Tetra-4-[4'-(4"-acetamidophenylazo)phenoxy]-
phthalocyanine cobalt (IXc) was obtained along the
general procedure using 0.81 g of 4-[4'-(4"-acet-
amidophenylazo)phenoxy]phthalonitrile and 0.19 g of
cobalt chloride. Yield 1.89 g (29.75%). Found, %: C
66.63, H 4.00, N 17.38. C88H60CoN20O8. Calculated,
%: C 66.71, H 3.82, N 17.68. EAS in DMF, λmax, nm:
365, 605, 667; in acetone, λmax, nm: 365, 600, 665, in
concentrated sulfuric acid, λmax, nm: 472, 710, 802.
Tetra-{4-[4'-(4"-methylphenylazo)phenoxy]}copper
phthalocyanine (Xa) was obtained along the general
procedure using 0.34 g of 4-[4-(4'-methylphenylazo)
phenoxy]phthalonitrile and 0.20 g of copper chloride.
Yield 1.91 g (32.62%). Found, %: C 71.10, H 4.25, N
15.68. C84H56CuN16O4. Calculated, %: C 71.20, H
3.98, N 15.82. EAS in chloroform, λmax, nm: 345, 613,
674; in DMF, λmax, nm: 345, 610, 675; in concentrated
sulfuric acid, λmax, nm: 470, 740, 839.
form, λmax, nm: 350, 605, 640, 665, 700; in DMF, λmax
,
nm: 359, 605, 637, 669, 697; in concentrated sulfuric
acid, λmax, nm: 475, 841, 901.
Tetra-4-[4'-(4"-acetamidophenylazo)phenoxy]-
phthalocyanine (VIIIc) was obtained along the
general procedure using 0.81 g of 4-[4'-(4"-acetamino-
phenylazo)phenoxy]phthalonitrile. Yield 2.63 g (43.13%).
Found, %: C 69.03, H 4.20, N 18.28. C88H62N16O8.
Calculated, %: C 69.19, H 4.09, N 18.38. EAS in
DMF, λmax, nm: 366, 610, 635, 669, 700; in acetone,
λ
max, nm: 369, 610, 639, 667, 699; in concentrated
sulfuric acid, λmax, nm: 470, 767, 817, 873.
Synthesis of metal complexes of tetra-R-phenyl-
azophnoxyphthalocyanines (general procedure). In
the glass tube was placed the required amount of a
ground mixture of 0.001 mole of the corresponding R-
Tetra-4-[4'-(2',4"-dimethylphenylazo)phenoxy]-
phthalocyanine copper (Xb) was obtained along the
general procedure using 0.35 g of 4-[4'-(2',4"-di-
methylphenylazo)phenoxy]phthalonitrile and 0.20 g of
copper chloride. Yield 1.78 g (31.54%). Found, %: C
71.61, H 4.51, N 15.16. C88H64CuN16O4. Calculated,
phenylazophnoxyphthalonitrile
VIIa–VIIc
and
0.0015 mol of a metal chloride, the tube was heated to
185–195°C and maintained at this temperature for 1 h.
After cooling, the reaction mixture was ground and
dissolved in concentrated sulfuric acid. The resulting
solution was poured on ice. The precipitate was
filtered off on a glass frit filter, and washed with water
until neutral reaction. Then the obtained powder was
washed with acetone in a Soxhlet apparatus and the
final purification was performed by column chro-
matography on silica gel, M 60, using as eluent
chloroform (IXa, IXb–XIa, XIb) or DMF (IXc–XIc).
%: C 71.75, H 4.38, N 15.21. EAS in chloroform, λmax
,
nm: 344, 615, 681; in DMF, λmax, nm: 355, 610, 675;
in concentrated sulfuric acid, λmax, nm: 476, 740, 846.
Tetra-4-[4'-(4"-acetamidophenylazo)phenoxy]-
phthalocyanine copper (Xc) was obtained along the
general procedure using 0.81 g of 4-[4'-(4"-acetamido-
phenylazo)phenoxy]phthalonitrile and 0.20 g of copper
chloride. Yield 1.99 g (35.30%). Found, %: C 66.58, H
4.10, N 17.42. C88H60CuN20O8. Calculated, %: C
Tetra-{4-[4'-(4"-methylphenylazo)phenoxy]}-
cobalt phthalocyanine (IXa) was obtained along the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

SYNTHESIS AND PROPERTIES OF PHTHALONITRILES
123
Vorob’ev, Yu.G., and Islyaikin, M.K., Izv. vuzov. Khim.
i Khim. Tekhnol., 2005, vol. 48, no. 7, p. 22.
3. Atsay, A., Özceşmeci, I., Okur, A.I., and Gül, A., J. Por-
phyrins and Phthalocyanines, 2008, vol. 12, nos. 3–6,
p. 451.
4. Tikhomirova, T.V., Badaukaite, R.A., Kulinich, V.P.,
and Shaposhnikov, G.P., Zh. Obshch. Khim., 2011,
vol. 81, no. 11, p. 1904.
5. Tikhomirova, T.V., Badaukaite, R.A., Kulinich, V.P.,
and Shaposhnikov, G.P., Abstract of Papers, XXV Int.
Conf. on Coordination Chemistry and II Youth Conf.-
School on Physico-Chemical Methods in the Chemistry
of Coordination Compounds, Ivanovo, 2011, p. 139.
66.51, H 3.81, N 17.63. EAS in DMF, λmax, nm: 365,
610, 675; in concentrated sulfuric acid, λmax, nm: 470,
725, 824.
Tetra-{4-[4'-(4"-methylphenylazo)phenoxy]}-
phthalocyanine nickel (XIa) was obtained along the
general procedure using 0.34 g of 4-[4-(4'-methyl-
phenylazo)phenoxy]phthalonitrile and 0.19 g of nickel
chloride. Yield 1.93 g (30.54%). Found, %: C 71,40, H
4,20, N 15,67. C84H56N16NiO4. Calculated, %: C 71.45,
H 4.00, N 15.87. EAS in chloroform, λmax, nm: 351,
616, 671; in DMF, λmax, nm: 341, 616, 672; in
concentrated sulfuric acid, λmax, nm: 470, 722, 814.
6. Stepanov, B.I., Vvedenie v khimiyu i tekhnologiyu
organicheskikh krasitelei (Introduction to the Chemistry
and Thechnology of Dyes), Moscow: Khimiya, 1984.
Tetra-4-[4'-(2',4"-dimethylphenylazo)phenoxy]-
phthalocyanine nickel (XIb) was obtained along the
general procedure using 0.35 g of 4-[4'-(2',4"-di-
methylphenylazo)phenoxy]phthalonitrile and 0.19 g of
nickel chloride. Yield 1.39 g (23.70%). Found, %: C
71.91, H 4.50, N 15.06. C88H64N16NiO4. Calculated,
7. Shishkina, O.V., Maizlish, V.E., and Shaposhnikov, G.P.,
Zh. Obshch. Khim., 1997, vol. 67, no. 5, p. 842.
8. Shaposhnikov, G.P. and Maizlish, V.E., Izv. Vuzov. Ser.
Khim. i Khim. Tekhnol., 2004, vol. 47, no. 5, p. 26.
9. Kulinich, V.P., Shaposhnikov, G.P., and Badaukaite, R.A.,
%: C 71.99, H 4.39, N 15.26. EAS in chloroform, λmax
,
Makrogeterots., 2010, vol. 3, no. 1, p. 23.
nm: 340, 610, 675; in DMF, λmax, nm: 363, 605, 673;
in concentrated sulfuric acid, λmax, nm: 480, 727, 821.
10. Shein, S.M., Doctorate (Chem.) Dissertation, Novo-
sibirsk, 1970.
Tetra-4-[4'-(4"-acetamidophenylazo)phenoxy]-
phthalocyanine nickel (XIc) was obtained along the
general procedure using 0.81 g of 4-[4'-(4"-acet-
amidophenylazo)phenoxy]phthalonitrile and 0.19 g of
nickel chloride. Yield 1.66 g (28.43%). Found, %: C
66.50, H 4.07, N 17.452. C88H60N20NiO8. Calculated,
%: C 66.72, H 3.82, N 17.68. EAS in DMF, λmax, nm:
350, 610, 677; in concentrated sulfuric acid, λmax, nm:
470, 725, 800.
11. Dyer, J.R., Application of Absorption Spectroscopy of
Organic Compounds, Moscow: Khimiya, 1970.
12. Sidorov, A.N. and Kotlyar, I.P., Opt. i Spektr., 1961,
vol. 11, no. 2, p. 175.
13. Porfiriny: spektroskopiya, elektrokhimiya, primenenie
(Porphyrines: Spectroscopy, Electrochemistry, and
Application), Enikolopyan, N.S., Ed., Moscow: Nauka,
1987.
14. Shaposhnikov, G.P., Maizlish, V.E., and Kulinich, V.P.,
Zh. Obshch. Khim., 2005, vol. 75, no. 11, p. 1916.
REFERENCES
15. Terenin, A.R., Fotonika molekul krasitelei i rod-
stvennykh soedinenii (Photonics of the Molecules of
Dyes and Related Compounds), Leningrad: Nauka, 1967.
16. Berezin, B.D., Koordinatsionnye soedineniya porfirinov
i ftalotsianina (Coordination Compounds of Porphyrin
and Phthalocyanine), Moscow: Nauka, 1978.
1. The Porphirin Handbook, Kadish, K.M., Smith, K.M.,
and Guilard, R., Eds., New York: Academic Press,
2003, vol. 15.
2. Shaposhnikov, G.P., Maizlish, V.E., Kulinich, V.P.,
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