Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: XI. Preparation, properties, and prediction of mesomorphism in mixed-substituted phthalocyanines containing aryloxy and benzotriazole fragments

Article abstract of DOI:10.1134/S1070363214040185

Stepwise nucleophilic substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile has led to a series of phthalonitriles containing benzotriazole and aryloxy fragments; basing on them, the mixed-substituted phthalocyanines have been prepare

Full text of DOI:10.1134/S1070363214040185

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 4, pp. 708–714. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Znoiko, O.B. Akopova, N.V. Bumbina, N.V. Usoltseva, V.E. Maizlish, G.P. Shaposhnikov, I.G. Abramov, 2014, published in
Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 4, pp. 629–636.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
XI.1 Preparation, Properties, and Prediction of Mesomorphism
in Mixed-Substituted Phthalocyanines Containing Aryloxy
and Benzotriazole Fragments
S. A. Znoikoa, O. B. Akopovab, N. V. Bumbinab, N. V. Usoltsevab,
V. E. Maizlisha, G. P. Shaposhnikova, and I. G. Abramovc
a Research Institute of Macroheterocycles, Ivanovo State Chemical-Technological University,
Sheremetevski pr. 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
b Research Institute of Nanomaterials, Ivanovo State University, Ivanovo, Russia
e-mail: n_bumbina@mail.ru
c Yaroslavl State Technical University, Yaroslavl, Russia
e-mail: abramovig@ ystu.ru
Received July 25, 2013
Abstract―Stepwise nucleophilic substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile
has led to a series of phthalonitriles containing benzotriazole and aryloxy fragments; basing on them, the
mixed-substituted phthalocyanines have been prepared. The spectral properties of products have been studied.
According to simulation of columnar mesomorphism only one of the products is not capable of mesomorphism
characteristic of discotic mesogens; the result has been confirmed with the experiment.
Keywords: phthalocyanine, simulation, mesomorphism, molecular descriptor
DOI: 10.1134/S1070363214040185
Phthalocyanines, synthetic analogs of natural
heterocyclic porphyrins, are attractive as promising
dyes, catalysts, and sensor materials [2–4]. Moreover,
phthalocyanines and their derivatives, basing on the
physicochemical properties, can be applied as
photoconductive materials in laser printers, LCDs,
optical recording devices, optical light diodes, and as
liquid crystals with one-dimensional conductivity [4].
phenols using the procedures reported elsewhere [5, 6].
The products I–V are white or light-beige powders,
insoluble in water and soluble in DMF, chloroform,
and acetone. Their melting points are above 200°С.
Following the procedure described in [7], benzo-
triazolyl-substituted phthalocyanines VI–X were pre-
pared by heating of phthalonitriles I–V with urea at
180–220°С. Urea was introduced into the reaction
mixture in order to decrease its melting point and
increase the products yield (Scheme 1).
In this work we report on preparation, spectral pro-
perties, and mesomorphism of a series of new
benzotriazolyl-substituted phthalocyanines.
The products were further extracted from the
reaction mixtures with chloroform and purified by
column chromatography on alumina (chloroform as
eluent).
Phthalonitriles I–V were prepared from 4-bromo-5-
nitrophthalonitrile via nucleophilic substitution of
bromine with ortho-phenylenediamine with subsequent
cyclization into benzotriazole fragment and nucleo-
philic substitution of nitro group with substituted
Yields of the purified derivatives VI–X were of 70–
80%. The products were dark-green, insoluble in water
and readily soluble in benzene, chloroform, acetone,
and DMF. Their structures were confirmed by
1 For communication X, see [1].
708

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XI.
709
Scheme 1.
NH2
H2N
N
Br
CN
CN
HN
CN
CN
NH2
KNO2 + CH3COOH
N
N
CN
O2N
O2N
O2N
CN
ROH
N
N
RO
N
4
5
3
urea 180_210°C
6
2 h
N
2
N
N
N
N
N
N
N
CN
N
OR
N
N
NH
HN
RO
N
CN
1
RO
N
N
N
I_V
N
OR
N
N
VI_X
11
10 11
10
8
8
11
11
8
8
10
10
7
7
7
7
9
12
(I, VI),
(II, VII),
(V, Х).
12 (III, VIII),
R =
*
*
*
11
9
13
9
10
10
10
9
7
7
8
*
*
NO2
8
8
11
10
9
9
(IV, IХ),
7
7
10
O
O
8
9
1
elemental analysis, Н NMR, IR, and electron absorp-
tion spectra.
upfield signals at –2.10 to –1.85 ppm were singlets of
the transannular imino groups; most of the signals
appearing as singlets in the phthalonitriles spectra were
broadened and split due likely to the formation of
mixture of isomers.
By the number and position of the signals 1Н NMR
spectra of phthalocyanines VI–X were quite similar to
those of phthalonitriles I–V. The main difference was
as follows: In the spectra of phthalocyanines the signal
of protons in position 1 was shifted upfield, the most
In the IR spectra of compounds VI–X no absorp-
tion bands were found at 2230–2240 cm–1 (range of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

710
ZNOIKO et al.
bands (Table 1); the shift was the most prominent in
D
the cases of products VI and VII and the least
significant in the case of derivative VIII.
In order to study theoretically the structure and
properties of liquid crystals, various modeling and
simulation methods are used [10–12]; mesomorphism
can be predicted as well using certain molecular
descriptors [13] and parameters [14–17].
Previously, we reported on mesomorphism of mixed-
substituted phthalocyanines containing peripheral
benzotriazolyl groups [18, 19]. An approach to predict
mesomorphism applying the molecular parameters
used in this work was similar to that discussed in [20].
λ, nm
Molecular models were constructed and optimized
utilizing HyperChem software package (molecular
mechanics ММ+ method, see results in Fig. 2). The
extracted geometry parameters formed the input of the
original CMP ChemСard software.
Fig. 1. Electron absorption spectra of solutions of com-
pound IX in DMF (1), chloroform (2), and concentrated
sulfuric acid (3).
nitrile group stretching vibrations) thus confirming that
the products were free of the staring materials.
The ability of the studied compounds to form
columnar and nematic mesophases was described by
the calculated molecular parameters with the typical
threshold values: K 2–8.5, Kc 1–2.6, Kp 0.2–0.7, Ks
0.25–1.00, Mm 0.2–0.8, Mr 0.15–0.80, and Kar 0.08–
0.30 (Table 2). Even a single parameter outside the
desired range indicated that the compound could not
form the mesophases typical of discotic mesogens.
Data in Table 2 show that four of the studied phthalo-
cyanines (VI, VII, IX, and X) can form the above-
mentioned mesophases.
Electron absorption spectra of compounds VI–X in
chloroform contained two intense long-wave absorp-
tions at around 675 nm and 710–711 nm (Fig. 1 and
Table 1) typical of phthalocyanines [8].
Spectra of the same compounds in DMF contained
instead of two long-wave bands a single Q-band at
around 680 nm (Fig. 2), confirming the formation of di-
anion form of phthalocyanine in the basic solvent [9].
Compounds IX and X could be re-precipitated from
concentrated sulfuric acid with their properties
preserved, whereas products VI–VIII were sulfonated
under similar conditions yielding water-soluble products.
In order to confirm the theoretical findings, the
prepared phthalocyanines VI–X were studied with
thermal polarization microscopy (Figs. 3 and 4).
Indeed, four of the products were transformed into
anisotropic state upon vitrification, thus revealing their
hidden (latent) thermotropic mesomorphism and
confirming the theoretical predictions (Table 2).
Solutions of compounds VI–X in concentrated
sulfuric acid, as compared with those in organic sol-
vents, revealed significant red shift of the absorption
Table 1. Absorption bands in electronic spectra of compounds VI–X
λmax, nm (log ε) (intensity ratio)
Comp. no.
DMF
chloroform
conc. H2SO4
VI
681
675 (5.06), 711 (5.14)
675 (4.93), 711 (5.02)
675 (4.92), 710 (5.00)
675 (4.99), 710 (5.08)
677 (4.90), 711 (4.98)
792, 831 [0.92 : 1]
795, 836 [0.87 : 1]
805
VII
VIII
IX
679
680 (4.82)
681
785, 827 [0.86 : 1]
781, 826 [0.87 : 1]
X
678
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XI.
711
VI
VII
VIII
IX
X
Fig. 2. Optimized geometry of molecules of compounds VI–X.
In particular, phthalocyanine VI became isotropic
liquid at heating to 150°С. During cooling, the molten
sample vitrified at 150–149°С as seen from the cracks
net appeared at 50°С (Fig. 3a). Upon further cooling,
the anisotropic rainbow broad pattern and dark blurs
were seen (the so called “leopard spots” [20]) (Fig. 3b).
Compound VII could be molten into isotropic
liquid as well at 180–185°С, being partially
decomposed. Its cooling to 100°С revealed the
cracks net showing vitrification, upon further cool-
ing the well defined anisotropic domains were seen
(Figs. 4a, 4b).
Table 2. Calculated molecular parameters of compounds VI–X and mesomorphism predictiona
Comp. no.
Е, kcal/mol
Mm
Mr
K
Kp
Kar
PCol+N
VI
159.87
165.14
140.16
135.43
133.13
0.48
0.48
0.51
0.50
0.43
0.24
0.24
0.26
0.25
0.22
2.49
2.32
1.89
2.59
2.52
0.59
0.57
0.62
0.58
0.51
0.25
0.29
0.26
0.21
0.18
+
+
–
VII
VIII
IX
+
+
X
a
For all the studied compounds, Ks = 0.5 and Kс = 1.33. PCol+N points at possibility of mesomorphism typical of discotic mesogens
(“–” impossible, ”+” possible).
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712
ZNOIKO et al.
(а)
(b)
Fig. 3. Texture of glassy phthalocyanine VI upon cooling cycle: (a) is network of cracks at 50ºС; (b) are traces of stress (“leopard
spots”) at 25ºС. Nicol prisms are parallel.
(а)
(b)
(c)
(d)
Fig. 4. Texture of glassy phthalocyanines (a, b) VII, (c) IX, and (d) (X) upon cooling cycle. Observation conditions: (a) Nicol
prisms parallel, (b–d) Nicol prisms transposed; temperature, ºС: (a) 85, (b) 65, (c) 25, and (d) 28.
Similar behavior was observed in the cases of
phthalocyanines IX and X. Compound IX formed the
isotropic liquid at 140°С, the cracks network upon
cooling appeared at 40°С, and the “leopard spots”
were seen at room temperature (Fig. 4c). Compound X
turned into isotropic melt at 187°С, and vitrified to
form the anisotropic texture upon cooling (Fig. 4d).
Hence, using the mixed-substituted phthalocyanine
bearing benzotriazolyl and aryloxy groups as an
example, we demonstrated the prediction of meso-
morphism from theoretical modeling.
EXPERIMENTAL
Electron absorption spectra (325–900 nm, room
temperature) were recorded using the HitachiU-2001
spectrophotometer. IR spectra (thin films from eva-
porated chloroform solutions, 400–4000 cm–1) were re-
gistered using the Avatar 360 FT-IR ESP spectrometer.
Compound VIII softened at 150°С and at higher
temperature could be molten into isotropic liquid (236°С).
Its cooling to below 170°С caused vitrification, but no
anisotropic mesophase was formed.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XI.
713
1Н NMR spectra (5 wt % in CDCl3, TMS as internal
reference) were obtained on a Bruker DRX-500
spectrometer. Elemental analysis was performed on a
CHNS-O FlashEA, 1112 series elemental analyzer.
1Н), 8.23 s (Н3, 1Н), 8.17 s (Н2, 1Н), 8.05 s (Н6, 1Н),
7.78–7.81 m (Н4, 1Н), 7.55–7.51 s (Н5, 1Н), 6.92–6.95
m (Н7,8, 2Н), 7.36 m (Н9,10, 2Н), 7.28 s (Н11, 2Н).
Found, %: С 72.65; Н 3.71; N 15.50. C27H17N5O.
Calculated, %: С 73.13; Н 3.86; N 15.79.
Mesomorphic properties of the prepared com-
pounds were observed with the MIN-8 optical polari-
zation microscope equipped with specially designed
temperature-controlled stage.
4-(1-Benzotriazolyl)-5-[4-(4-nitrophanoxy)phen-
oxy]phthalonitrile (IV) was prepared from 0.230 g of
4-(4-nitrophenoxy)phenol. Yield 0.43 g (91%), mp
220–222°С. IR spectrum, ν, cm–1: 1560 [νas(NO2)],
1354 [νs(NO2)], 1220 (Ar–O–Ar), 1045 (N=N), 743
4-Bromo-5-nitrophthalonitrile was obtained as des-
cribed in [21] and was used for further synthesis of 4-
(1-benzotriazolyl)-5-nitrophthalodinitrile [5].
1
(C–N). Н NMR spectrum, δ, ppm: 8.97 s (Н10, 1Н),
8.70 s (Н1, 1Н), 8.30 s (Н3, 1Н), 8.18 s (Н2, 1Н), 8.04 s
(Н6, 1Н), 7.80 s (Н4, 1Н), 7.40–7.51 m (Н5, 1Н), 6.98 s
(Н7, 1Н), 7.04 s (Н8, 1Н), 6.83–7.00 m (Н9, 1Н).
Found, %: С 65.60; Н 3.30; N 17.80. C26H14N6O.
Calculated, %: С 65.80; Н 2.97; N 17.71.
4-(1-Benzotriazolyl)-5-(4-cyclohexylphenoxy)-
phthalonitrile (III) was prepared as described in [22].
Preparation of phthalonitriles (I, II, IV, V). A
mixture of 1 mmol of the corresponding substituted
phenol and 1 mmol (0.290 g) of 4-(1-benzotriazolyl)-
5-nitrophthalonitrile was dissolved in 5 mL of DMF,
then 0.138 g (1 mmol) of potassium carbonate in 2 mL
of water was added to the solution. The mixture was
maintained at room temperature during 1 h. The
precipitate was filtered off, washed with water and
isopropanol, and dried at 60°С.
Phthalocyanines VI–X were prepared by heating
of 0.45 mmol of the corresponding substituted
phthalonitrile I–V in the presence 10 mg (0.166 mmol)
of urea during 2 h. The target products were extracted
with chloroform and then purified by column chroma-
tography (alumina, chloroform as eluent). After the
solvent evaporation the products were dried at 60–80°С.
4-(1-Benzotriazolyl)-5-[4-(3-methylphenyl)-2-
methylphenoxy]phthalonitrile (I) was prepared from
0.198 g of 4-(3-methylphenyl)-2-methylphenol. Yield
0.39 g (88%), mp 210–212°С. IR spectrum, ν, cm–1:
1221 (Ar–O–Ar), 2228 (C≡N), 1045 (N=N), 745 (C–N).
1Н NMR spectrum, δ, ppm: 8.71 s (Н1, 1Н), 8.13 s (Н3,
1Н), 8.25 s (Н2, 1Н), 8.05 s (Н6, 1Н), 7.78–7.80 m (Н4,
Tetra-4-(1-benzotriazolyl)tetra-5-[4-(3-methyl-
phenyl)-2-methylphenoxy]phthalocyanine (VI) was
prepared from 200 mg of I at 185°С. Yield 156 mg
(79%). IR spectrum, ν, cm–1: 3071 (N–H), 2830, 2845
(CH3), 1210 (Ar–O–Ar), 1047 (N=N), 1009 (H2Pc),
1
745 (C–N). Н NMR spectrum, δ, ppm: 8.51 m (Н1,
4Н), 8.27 m (Н3, 4Н), 8.22 m (Н2, 4Н), 8.18 m (Н6,
4Н), 7.71 m (Н4, 4Н), 7.49–7.61 m (Н5, 4Н), 7.43 m
(Н8, 4Н), 7.28 m (Н7,10,11, 12Н), 7.20 s (Н9, 4Н), 7.09
m (Н12,13, 4Н), 2.31–2.44 m (СН3, 12Н), 1.85 s
(NHtransannul, 2Н). Found, %: С 76.46; Н 4.40; N 15.58.
C112H78N20O4. Calculated, %: С 76.09; Н 4.45; N 15.84.
1Н), 7.50 s (Н5, 1Н), 7.33 s (Н8, 1Н), 7.38 m (Н7,10,11
,
3Н), 7.12 s (Н9, 1Н), 7.29 m (Н12,13, 2Н), 2.24–2.30 m
(СН3, 6Н). Found, %: С 75.60; Н 4.31; N 15.80.
C28H19N5O. Calculated, %: С 76.18; Н 4.34; N 15.86.
4-(1-Benzotriazolyl)-5-[4-(4-methylphenyl)-2-
methylphenoxy]phthalonitrile (II) was prepared
from 0.200 g of 4-(4-methylphenyl)-2-methylphenol.
Yield 0.38 g (86%), mp 210–212°С. IR spectrum, ν,
Tetra-4-(1-benzotriazolyl)tetra-5-[4-(4-methyl-
phenyl)-2-methylphenoxy]phthalocyanine (VII) was
prepared from 198 mg of II at 185°С. Yield 160 mg
(79%). IR spectrum, ν, cm–1: 3070 (N–H), 1212 (Ar–
1
cm–1: 1217 (Ar–O–Ar), 1045 (N=N), 746 (C–N). Н
NMR spectrum, δ, ppm: 8.71 s (Н1, 1Н), 8.23 m (Н3,
1Н), 8.13 s (Н2, 1Н), 8.00 m (Н6,9, 2Н), 7.79 s (Н4,
2Н), 7.53 m (Н5, 10, 2Н), 7.40 s (Н7, 1Н), 7.20 s (Н11,
1Н), 2.24–2.34 m (СН3, 6Н). Found, %: С 76.50; Н
4.13; N 16.08. C28H19N5O. Calculated, %: С 76.18; Н
4.34; N 15.86.
1
O–Ar), 1045 (N=N), 1007 (H2Pc), 744 (C–N). Н
NMR spectrum, δ, ppm: 8.51 s (Н1), 8.21 m (Н3, 4Н),
8.18 s (Н2, 4Н), 8.10 m (Н6,9, 8Н), 7.72 m (Н4, 4Н),
7.61 m (Н10, 4Н), 7.52 m (Н5, 4Н), 7.36 m (Н7, 4Н),
7.21 m (Н11, 4Н), 2.21–2.44 m (СН3, 12Н), –1.89 s
(NHtransannul, 2Н). Found, %: С 76.31; Н 4.02; N 15.18.
C112H78N20O4. Calculated, %: С 76.09; Н 4.45; N 15.84.
4-(1-Benzotriazolyl)-5-(4-oxyphenylphenoxy)-
phthalonitrile (III) was prepared from 0.185 g of 4-
oxyphenylphenol. Yield 0.37 g (86%), mp 205–208°С.
IR spectrum, ν, cm–1: 1220 (Ar–O–Ar), 1045 (N=N),
Tetra-4-(1-benzotriazolyl)tetra-5-[4-cyclohexyl-
phenoxy]phthalocyanine (VIII) was prepared from
185 mg of III at 210°С. Yield 148 mg (74%). IR
1
745 (C–N). Н NMR spectrum, δ, ppm: 8.73 s (Н1,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

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ZNOIKO et al.
spectrum, ν, cm–1: 3071 (N–H), 1220 (Ar–O–Ar), 1041
(N=N), 1015 (H2Pc), 744 (C–N). 1Н NMR spectrum, δ,
ppm: 8.63 m (Н1, 4Н), 8.24 m (Н3, 4Н), 8.16 s (Н2,
4Н), 8.04 m (Н6, 4Н), 7.69 m (Н4, 4Н), 7.59 m (Н5,
4Н), 7.21 m (Н8, 4Н), 7.03 m (Н7, 4Н), 2.90 m (Н9,
4Н), 1.89 m (Н10, 4Н), 1.40 s (Н11, 4Н), –2.00 s
(NHtransannul, 2Н). Found, %: С 74.13; Н 4.92; N 16.18.
C104H86N20O4. Calculated, %: С 74.44; Н 5.05; N 16.70.
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i ftalotsianina (Coordination Compounds of Porphyrin
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9. Vul’fson, S.V., Lebedev, O.L., and Luk’yanets, E.A.,
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nauch.-prakt. konf. “Sovremennye problemy i puti ikh
Tetra-4-(1-benzotriazolyl)tetra-5-[4-oxyphenyl-
phenoxy]phthalocyanine (IX) was prepared from 195
mg of IV at 205°С. Yield 153 mg (77%). IR spectrum,
ν, cm–1: 3071 (N–H), 1218 (Ar–O–Ar), 1045 (N=N),
1
1010 (H2Pc), 746 (C–N). Н NMR spectrum, δ, ppm:
8.61 s (Н1, 4Н), 8.25 m (Н3, 4Н), 8.19 s (Н2, 4Н), 8.04
m (Н6, 4Н), 7.68 m (Н4, 4Н), 7.58 m (Н5, 4Н), 7.45 s
(Н9, 4Н), 7.38 m (Н10,11, 8Н), 7.03–7.06 m (Н7,8, 8Н),
–1.89 s (NHtransannul, 2Н). Found, %: С 67.84; Н 3.67;
N 14.19. C104H86N20O4. Calculated, %: С 68.52; Н
3.20; N 14.81.
Tetra-4-(1-benzotriazolyl)tetra-5-[4-(4-nitrophen-
oxy)phenoxy]phthalocyanine (X) was prepared from
215 mg of V at 230°С. Yield, 140 mg (70%). IR
spectrum, ν, cm–1: 3071 (N–H), 1218 (Ar–O–Ar), 1546
[νas(NO2)], 1356 [νs(NO2)], 1045 (N=N), 1010 (H2Pc).
1Н NMR spectrum, δ, ppm: 8.97 s (Н10, 4Н), 8.57 s
(Н1, 4Н), 8.32 m (Н3, 4Н), 8.19 s (Н2, 4Н), 8.04 s (Н6,
4Н), 7.62 m (Н4, 4Н), 7.40–7.51 m (Н5, 4Н), 6.98 m
(Н7, 4Н), 7.04 s (Н8, 4Н), 6.73–7.06 m (Н, 4Н9), –2.09
s (NHtransannul, 2Н).
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (project no. 13-03-00481a).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014