Phthalocyanines and related compounds: XLVII. Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile. Synthesis of phenyl(alkyl)amino- substituted phthalonitriles and some phthalocyanines based thereon

Article abstract of DOI:10.1134/S1070363208090235

Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile by the action of primary and secondary amines was studied. The reactions of tetrachlorophthalonitrile with amines at a ratio of 1: 10 gave with high yields and regioselectivity the corresponding 4,5-diamino-3,6-dichlorophthalonitriles from cyclic secondary amines and 4-amino-3,5,6-trichlorophthalonitriles from primary amines and acyclic secondary amines. 4-Amino-3,5,6- trichlorophthalonitriles were used to synthesize cobalt and zinc phthalocyanine complexes. It was shown that replacement of chlorine atoms in the pyrrolic β-positions of hexadecachlorophthalocyanines by amino groups is not accompanied by red shift of the long-wave absorption band in the electronic spectra.

Full text of DOI:10.1134/S1070363208090235

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1787–1793. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © K.A. Volkov, G.V. Avramenko, V.M. Negrimovskii, E.A. Luk’yanets, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78,
No. 9, pp. 1557–1563.
Phthalocyanines and Related Compounds:
XLVII.1 Nucleophilic Replacement of Chlorine Atoms
in Tetrachlorophthalonitrile. Synthesis
of Phenyl(alkyl)amino-substituted Phthalonitriles
and Some Phthalocyanines Based Thereon
K. A. Volkova, G. V. Avramenkob, V. M. Negrimovskiia, and E. A. Luk’yanetsa
a Research Institute of Organic Intermediates and Dyes, ul. Bol’shaya Sadovaya 1/4, Moscow, 123995 Russia
e-mail: rmeluk@niopik.ru
b Mendeleev Russian University of Chemical Technology, Moscow, Russia
Received February 1, 2008
Abstract—Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile by the action of primary
and secondary amines was studied. The reactions of tetrachlorophthalonitrile with amines at a ratio of 1:10
gave with high yields and regioselectivity the corresponding 4,5-diamino-3,6-dichlorophthalonitriles from
cyclic secondary amines and 4-amino-3,5,6-trichlorophthalonitriles from primary amines and acyclic secondary
amines. 4-Amino-3,5,6-trichlorophthalonitriles were used to synthesize cobalt and zinc phthalocyanine
complexes. It was shown that replacement of chlorine atoms in the pyrrolic β-positions of
hexadecachlorophthalocyanines by amino groups is not accompanied by red shift of the long-wave absorption
band in the electronic spectra.
DOI: 10.1134/S1070363208090235
compound I with some primary and secondary amines
(Scheme 1, Table 1) with a view to obtain amino-
substituted phthalonitriles and use the latter to obtain
the corresponding phthalocyanines.
Amino-substituted phthalonitriles are initial
compounds for the synthesis of phthalocyanines. They
can be prepared by nucleophilic replacement of nitro
groups and halogen atoms in the corresponding nitro-
and halogen-substituted phthalonitriles by the action of
amines [2]. One amino group was introduced into the
benzene ring of phthalonitrile using 3- and 4-nitro- [3],
4-bromo- [3], 3-bromo-5-tert-butyl- [3] and 4,5-
dichlorophthalonitriles [4] as starting compounds.
Diamino derivatives were obtained from 4-bromo-5-
nitro- [5, 6] and 3,5-dinitrophthalonitriles [7]. Nucleo-
The reactions of dinitrile I with primary (aniline,
octylamine) and secondary amines (diethylamine,
dibutylamine, piperidine, morpholine) were carried out
at 50–80°C in DMF (reaction time 5 h) using
potassium carbonate or excess nucleophile as base.
The reactions of I with 2 equiv of primary and acyclic
secondary amines at 50°C in the presence of K2CO3
gave only monosubstituted products II–V in 39–45%
yield, and the conversion of dinitrile I was not
complete. Initial compound I may be recovered by 8–
12% from the reaction mixture by column
chromatography. In the reactions with cyclic secondary
amines, other conditions being equal, the conversion of
dinitrile I was complete, and the products were
philic
replacement
of
fluorine
atoms
in
tetrafluorophthalonitrile by amino groups gave the the
corresponding 4-mono- [8, 9] and 4,5-diamino-
phthalonitriles [9].
In continuation of our studies on nucleophilic
substitution of chlorine atoms in tetrachloro-
phthalonitrile (I) by the action of various nucleophiles
[10, 11], in the present work we examined reactions of
approximately
equimolar
mixtures
of
the
corresponding mono- (VI, VII), and diamino
derivatives (VIII, IX). All these products were isolated
1
For communication XLVI, see [1].
1787

1788
VOLKOV et al.
Scheme 1.
NR2R1
CN
Cl
Cl
Cl
R1R2N
R1R2 N
R1R2N
CN
CN
CN
Cl
Cl
CN
CN
Cl
R1R2NH
×
R1R2NH
+
DMF
50_80оС
DMF
150оС
R1R2N
R1R2 N
CN
CN
Cl
Cl
Cl
Cl
VIII, IX
II−VII
I
R1 = H, R2 = Ph (II), n-C8H17 (III); R1 = R2 = Et (IV), Bu (V); R1R2 = (CH2)2O(CH2)2 (VI, VIII), (CH2)5 (VII, IX).
as individual substances by column chromatography
and were identified on the basis of their elemental
compositions and NMR and mass spectra (Tables 2, 3).
An exception was 3,4,6-trichloro-5-piperidinophthalo-
nitrile (VII) which was detected by mass spectrometry
in a mixture with 3,6-dichloro-4,5-dipiperidinophthalo-
nitrile (IX).
nitrile and greater yield of monoamino derivatives II–
V in the reactions with primary and acyclic secondary
amines; the reaction of I with 4 equiv of morpholine
gave mainly disubstituted product VIII. The use of
even larger excess of amine (10 equiv) and raising the
temperature to 80°C resulted in complete conversion
of compound I even in the absence of potassium
carbonate, and in each case only one product was
formed in 58–65% yield. Monoamino-substituted
phthalonitriles II–V were obtained from aniline,
Increase in the amount of amine to a ratio of 1:4
ensured higher conversion of initial tetrachlorophthalo-
octylamine,
diethylamine,
and
dibutylamine,
Table 1. Yields of substitution products (%) in the reactions
of phthalonitrile I with amines at different reactant ratiosa
respectively, while morpholine and piperidine gave
rise to diaminodichlorophthalonitriles VIII and IX. No
replacement of the remaining chlorine atoms was
observed upon further increase of the amount of amine
and reaction temperature.
Molar ratio dinitrile
I–R1R2NH
Comp.
no.
R1
R2
1:2 b
11.2
38.7
12.3
42.3
7.6
1:4 b
6.0
1:10
–
It should be noted that the reaction of
tetrafluorophthalonitrile with primary adamantan-1-
amine resulted in the formation of both mono- and
disubstituted products [9]. Presumably, the reactivity
of fluorine atoms in tetrafluorophthalonitrile is higher
than the reactivity of chlorine atoms in
tetrachlorophthalonitrile (I). Introduction of two strong
electron-donating amino groups is likely to
compensate electron-withdrawing effect of the cyano
groups, so that further nucleophilic replacement of
halogen atoms becomes impossible. Therefore, no
products of substitution by amino groups of three and
the more so four halogen atoms in both
tetrafluorophthalonitrile and tetrachlorophthalonitrile
(I) were formed.
Ph
H
I
59.7
65.0c
II
I
d
n-C8H17
Еt
H
–
54.6
58.3c
–
III
I
Еt
Вu
45.2
9.7
60.0c
IV
I
d
Вu
–
43.5
52.9
V
64.3c
–
CH2CH2OCH2CH2
(CH2)5
40.5
10.8
47.6
VI
30.3
65.5c
VIII
VII
IX
e
–
Thus aromatic nucleophilic substitution in
tetrachlorophthalonitrile (I) makes it possible to obtain
products of replacement by amino groups of
maximally two chlorine atoms; in contrast, three
chlorine atoms in tetrachlorophthalonitrile (I) can be
replaced by aroxy groups [11], and four chlorine
atoms, by sulfanyl groups [10].
36.2
61.7c
a
Unless otherwise stated, given are yields of products isolated by
b
column chromatography (silica gel, eluent toluene).
In the
presence of K2CO3 as base. c After recrystallization from ethanol.
d
e
Traces (according to the TLC data).
Identified by mass
spectrometry in a mixture with compound IX.
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PHTHALOCYANINES AND RELATED COMPOUNDS: XLVII.
1789
Table 2. Melting points, elemental analyses, and IR and mass spectral data for phthalonitriles
Elemental analysis data
Comp.
no.
νCN, cm–1 M+
Found, %
Calculated, %
mp, °С
Formula
C
H
Cl
N
C
H
Cl
N
220–222
64–66
51.97
52.10
1.88
1.93
32.89
33.15
12.90
13.07
C14H6Cl3N3
C16H18Cl3N3
C12H10Cl3N3
C16H18Cl3N3
C12H8Cl3N3O
C16H16Cl2N4O2
C18H20Cl2N4
52.13
1.87
32.97
13.03
2236
2233
2232
2235
2227
2224
2226
321
357
301
357
315
366
362
II
53.40
53.61
5.02
5.07
29.53
29.69
11.56
11.78
53.58
47.63
53.58
45.53
52.33
59.51
5.06
3.33
5.06
2.55
4.39
5.55
29.65
35.15
29.65
33.60
19.31
19.52
11.71
13.89
11.71
13.27
15.26
15.42
III
IV
V
121–122
98–100
124–125
173–175
195–196
47.55
47.70
3.24
3.30
35.00
35.23
13.81
13.97
53.43
53.61
5.00
5.09
29.46
29.74
11.61
11.68
45.40
45.69
2.53
2.60
33.54
33.71
13.19
13.36
VI
VIII
IX
52.22
52.43
4.40
4.44
19.16
19.35
15.17
15.33
59.33
59.64
5.45
5.53
19.40
19.66
15.34
15.48
Table 3. 13C and 1H NMR spectra of compounds II–IX in DMSO-d61
Comp.
1H NMR spectrum,
13C NMR spectrum, δС, ppm
no.
δH, ppm
143.5 (C' –N), 141.2 (CAr–N), 135.7 (CAr–Cl), 131.7 (CAr–Cl), 129.7 (CAr–Cl), 128.7 (C'Ar–H), 6.90 d (1H), 6.99 t (2H),
II
Ar
122.3 (C' –H), 118.4 (C'Ar–H), 116.6 (CAr–CN), 113.5 (C'Ar–H), 113.3 (CN), 109.4 (CN)
7.26 t (2H), 8.98 s (1H)
Ar
147.1 (CAr–N), 135.3 (CAr–Cl), 123.5 (CAr–CN), 121.6 (CAr–CN), 113.7 (CN), 113.2 (CN), 45.7 0.85 t (3H), 1.23 s (10H),
III
(CH2–N), 31.1 (CH2), 30.4 (CH2), 28.5 (CH2), 25.8 (CH2), 22.0 (CH2), 13.8 (CH3)
1.54–1.59 m (2H), 3.67–
3.57 q (2H), 6.78 t (1H)
150.7 (CAr–N), 139.4 (CAr–Cl), 136.7 (CAr–Cl), 135.5 (CAr–Cl), 116.3 (CAr–CN), 116.1 (CAr–CN), 0.98–1.07 m (6H), 3.21–
113.0 (CN), 112.3 (CN), 46.2 (CH2–N), 13.4 (CH3) 3.37 m (4H)
151.0 (CAr–N), 138.5 (CAr–Cl), 137.4 (CAr–Cl), 135.9 (CAr–Cl), 116.9 (CAr–CN), 116.5 (CAr–CN), 0.84 t (6H), 1.18–1.41 m
113.1 (CN), 111.8 (CN), 51.6 (CH2–N), 30.1 (CH2), 19.4 (CH2), 13.6 (CH3) (8H), 3.23 t (4H)
IV
V
152.9 (CAr–N), 136.9 (CAr–Cl), 135.8 (CAr–Cl), 134.4 (CAr–Cl), 116.5 (CAr–CN), 115.8 (CAr–CN), 3.28 t (4H), 3.75 t (4H)
113.1 (CN), 111.6 (CN), 69.1 (CH2–O), 52.5 (CH2–N)
VI
151.2 (CAr–N), 137.2 (CAr–Cl), 115.6 (CAr–CN), 114.5 (CN), 67.4 (CH2–O), 51.1 (CH2–N)
3.31 t (4H), 3.75 t (4H)
VIII
IX
154.6 (CAr–N), 139.0 (CAr–Cl), 115.5 (CAr–CN), 114.4 (CN), 51.0 (CH2–N), 25.8 (CH2), 23.3
(CH2)
Characteristically, replacement of both one and two
chlorine atoms by amino groups in each case led to the
formation of only one of the two possible
monosubstituted products and only one of the four
possible disubstituted products, i.e., the process was
regioselective, as in the reactions with thiolate [10] and
aroxide ions [11]. Analogous results were obtained in
the reactions of such amines as aniline [8] and
adamantan-1-amine [9] with tetrafluorophthalonitrile:
in each case only one mono- or disubstituted product
was obtained, 4-amino-3,5,6-trifluoro- or 4,5-diamino-
3,6-difluorophthalonitrile, respectively. Taking into
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1790
VOLKOV et al.
account these data, as well as the data of our previous
studies on the regioselectivity of chlorine replacement
in tetrachlorophthalonitrile (I) by other nucleophiles
[10, 11], we can assert that in the reaction with amines
the 4-chlorine atom is replaced first and that the
subsequent substitution occurs at the 5 position. The
13C NMR spectra of compounds VIII and IX confirm
their symmetric structure.
X–XIV (Scheme 2, Table 4) in ~40% yield. Their
elemental compositions were in agreement with the
assumed structure.
No phthalocyanine complexes were formed by
heating diaminodichloro derivatives VIII and IX with
metal salts in the presence of DBU on exposure to air.
When the reaction was carried out with protection
from atmospheric air, the mixture turned dark green.
Obviously, octaaminooctachlorophthalocyanines un-
dergo decomposition on exposure to atmospheric
oxygen, so that we failed to isolate the corresponding
complexes. We succeeded only in detecting long-wave
absorption maxima of the zinc complexes in the
electronic spectra of the reaction mixtures: λmax 719
and 722 nm in benzene for the morpholino- and
piperidino-substituted derivatives, respectively.
We also used benzene-1,2-diamine as nucleophile
with a view to obtain the corresponding dihydro-
phenazine or at least ortho-amino-substituted analog of
dinitrile II. However, the reaction at 50–100°C was
accompanied by tarring, whereas no reaction occurred
at lower temperature.
All tetrasubstituted phthalonitriles prepared in the
present work were used in the synthesis of the
corresponding hexadecasubstituted phthalocyanines.
We failed to isolate the target phthalocyanine metal
complexes under standard conditions for template
synthesis, i.e., by gradually heating substituted
phthalonitrile with a metal salt [cobalt(II) chloride or
zinc(II) acetate] in the presence of ammonium
molybdate from 140°C to 210°C and subsequently
keeping the mixture for several hours at that
temperature. On the other hand, tetraaminodo-
decachlorophthalocyanine complexes were formed
when monoaminophthalonitriles II–VI were heated in
boiling pentan-1-ol with metal salts in the presence of
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). After
chromatographic purification, we isolated complexes
Tetraaminododecachlorophthalocyanine cobalt and
zinc complexes X–XIV are green powders which are
soluble to a concentration of ~10–4 M on heating in
dipolar aprotic solvents (such as DMF and DMSO), as
well as in pyridine due to coordination of solvent
molecules at the central metal ion. Dialkylamino-
substituted complexes XII–XIV are also soluble (to a
greater or lesser extent) in some organic solvents (ethyl
acetate, chloroform, benzene, and hexane). For
example, the solubility of diethylamino derivatives XII
in ethyl acetate and of dibutylamino-substituted
complexes XIII in benzene reaches ~10–3 M, while
octylamino-substituted compounds XI in the same
solvents are soluble to a concentration of only ~10–5 M.
Scheme 2.
Cl
R
Cl
Cl
Cl
Cl
Cl
Cl
Cl
N
N
N
M
N
R
R
CN
CN
Cl
R
M2+, pentan-1-ol, DBU
N
N
Δ
Cl
Cl
N
N
Cl
II−VI
Cl
Cl
R
Cl
Х−ХIV
II, X, R = PhNH; III, XI, R = n-C8H17NH; IV, XII, R = Et2N; V, XIII, R = Bu2N; VI, XIV, R = morpholino; M = Co (a), Zn (b).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

PHTHALOCYANINES AND RELATED COMPOUNDS: XLVII.
1791
Table 4. Elemental analyses and long-wave absorption maxima in the electronic spectra of phthalocyanine complexes X–XIV
Elemental analysis data
Comp.
no.
λmax, nm
Found, %
Calculated, %
(benzene)
Formula
C
H
Cl
N
C
H
Cl
N
49.68
49.82
1.84
1.86
31.45
31.62
12.30
12.56
C56H24Cl12CoN12
49.85
1.79
31.53
12.46
703а
714а
708
719
704
714
705
716
707
718
Xа
49.48
49.69
1.80
1.85
31.17
31.33
12.20
12.44
C56H24Cl12N12Zn
C64H72Cl12CoN12
C64H72Cl12N12Zn
C48H40Cl12CoN12
C48H40Cl12N12Zn
C64H72Cl12CoN12
C64H72Cl12N12Zn
C48H32Cl12CoN12O4
C48H32Cl12N12O4Zn
49.61
51.46
51.24
45.42
45.19
51.46
51.24
43.50
43.29
1.78
4.86
4.84
3.18
3.16
4.86
4.84
2.43
2.42
31.38
28.48
28.36
33.52
33.35
28.48
28.36
32.10
31.95
12.40
11.25
11.20
13.24
13.18
11.25
11.20
12.68
12.62
Xb
51.29
51.54
4.91
4.95
28.31
28.52
11.16
11.33
XIа
51.18
51.32
4.86
4.94
28.26
28.37
11.11
11.32
XIb
45.37
45.46
3.09
3.16
33.58
33.66
13.08
13.34
XIIa
XIIb
XIIIа
XIIIb
XIVа
XIVb
In DMF.
45.09
45.20
3.07
3.15
33.21
33.44
13.10
13.27
51.36
51.57
4.89
4.93
28.38
28.59
11.14
11.33
51.22
51.33
4.78
4.83
28.29
28.46
11.05
11.19
43.37
43.57
2.37
2.46
32.00
32.18
12.54
12.76
43.08
43.26
2.43
2.47
31.77
32.09
12.55
12.72
a
Phenylamino- and octylamino-substituted phthalo-
diethylamino (XII), dibutylamino (XIII), and
morpholino derivatives (XIV) is well resolved, and a
number of vibrational satellites are present. The
spectra of phthalocyanines X and XI having secondary
amino groups on the macroring contain an absorption
band at λ ~720 nm, which corresponds to unassociated
molecules, and a band at ~680 nm due to absorption of
associates. The latter band is especially strong in the
spectra of XI. Obviously, aggregation of dye
molecules results from intermolecular hydrogen
bonding with participation of protons in the secondary
amino groups [12].
cyanine complexes X and XI are insoluble in con-
centrated hydrochloric acid; dibutylamino-substituted
analogs XIII are soluble in hydrochloric acid to a
spectral concentration level only on heating to the
boiling point. On the other hand, the solubility of
diethylamino derivatives XII in concentrated
hydrochloric acid attains ~10–4 M.
We measured the electronic absorption spectra of
complexes X–XIV in DMF (X) and benzene (XI–
XIV), and the spectra of zinc complexes XIIb and
XIIIb were also recorded in concentrated hydrochloric
acid. Like most phthalocyanine metal complexes,
compounds X–XIV in organic solvents displayed two
strong absorption bands in the region λ 300–850 nm:
the long-wave band (Q) was located at λ 703–708 and
714–719 nm for the cobalt and zinc complexes,
respectively, and the short-wave Soret band appeared
at λ 370–390 nm (Fig. 1). The Q band in the spectra of
The electronic absorption spectra of complexes XII
and XIII in concentrated hydrochloric acid remain
generally the same as in benzene. However, unlike
organic solvent, complexes XII and XIII in acid
medium exist mainly as associates, as follows from the
presence of a strong absorption band at λ 680 nm (Fig. 2).
In addition, diethylamino-substituted compound XIIb
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

1792
VOLKOV et al.
1.0
0.5
0.0
XIIIb
Xb
XIIb
XIVb
1.0
0.5
0.0
XIIIb
XIIb
XIb
550 600 650 700 750 800 850
350 400 450 500 550 600 650 700 750 800
λ, nm
λ, nm
Fig. 1. Electronic absorption spectra of complex Xb in DMF
and of complexes XIb–XIVb in benzene.
Fig. 2. Electronic absorption spectra of complexes XIIb and
XIIIb in 35% hydrochloric acid.
clearly displayed a band at λ 760 nm, indicating partial
protonation of the dye molecules at the meso-nitrogen
atoms [13].
weak effect of α-nitro groups in phthalocyanine as
compared to β-nitro groups [17]. Shaposhnikov et al.
[18] performed a molecular mechanics study which
showed that one of the two neighboring groups in the β
positions of phthalocyanines having four couples of
ortho substituents, e.g., a nitro group neighboring to
bromine atom or a phenoxy group neighboring to nitro
group, deviates from the macroring plane.
Furthermore, recent X-ray diffraction data revealed
noncoplanarity of substituents in two hexadeca-
substituted phthalocyanine derivatives [19].
The electronic absorption spectra of complexes X–
XIV are characterized by a considerable red shift of
the Q band as compared to their unsubstituted analogs
(the data for solutions of the latter in pyridine were
taken from [14]); the Δλ values are 45–50 nm for the
cobalt complexes and 42–47 nm for the zinc
complexes (Table 4). Obviously, the red shift is related
to the presence of both chlorine atoms [15, 16] and
alkylamino groups [3, 4] in the macroring. On the
other hand, replacement of four and even eight
chlorine atoms in zinc and cobalt hexadeca-
chlorophthalocyanines (λmax 711 and 706 nm in DMF,
respectively [16]) is not accompanied by appreciable
red shift of the long-wave Q band (taking into account
the observed absorption maxima for octaamino
derivatives). These findings seem to be somewhat
surprising since replacement of four β-chlorine atoms
in tetrachlorophthalocyanines [15] by alkylamino
groups leads to quite considerable shift of the Q band,
in particular by ~40 nm for cobalt complexes [14].
Thus, the following conclusions can be drawn from
the results of the present study: (1) reactions of
tetrachlorophthalonitrile with primary and secondary
amines could result in the formation of products of
replacement of no more than two chlorine atoms; (2)
the replacement process is regioselective: only chlorine
atoms in positions 4 and 5 are replaced; (3)
replacement of four chlorine atoms in the β positions
of hexadecachlorophthalocyanine cobalt and zinc
complexes by amino groups does not induce an
appreciable red shift of the long-wave absorption band
in the electronic spectra.
Such a weak effect of amino groups in tetra-
aminododecachlorophthalocyanines on the position of
the Q band may be rationalized in terms of steric
hindrances inducing rotation of the amino groups
about the N–CAr bond and hence loss of conjugation
between the aromatic system of the macroring and lone
electron pair on the amino nitrogen atom. An
analogous explanation was proposed previously for the
EXPERIMENTAL
The elemental compositions were determined using
a Hewlett–Packard HP–185B C,H,N analyzer. The IR
spectra were measured in KBr on an FSM 1201
spectrometer with Fourier transform. The mass spectra
(electron impact, 70 eV) were obtained on an MKh-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008

PHTHALOCYANINES AND RELATED COMPOUNDS: XLVII.
1793
1
1321 instrument. The H and 13C NMR spectra were
recorded on a Bruker AM-300 instrument from
solutions in DMSO-d6 using tetramethylsilane as
internal reference. The Electronic absorption spectra
were measured on a Varian Cary 50 spectrophotometer.
The reaction mixtures were analyzed, and the purity of
products was checked, by TLC on Silufol UV-254
plates.
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tetrachlorophthalonitrile (I), 1.75 or 3.5 g of potassium
carbonate, and the corresponding amine (0.01 or 0.02
mol in the presence of potassium carbonate or 0.05
mol in the absence of it) in 30 ml of DMF was stirred
for 5 h at 50°C or 80°C (in the absence of K2CO3). The
mixture was cooled, poured into a saturated solution of
sodium chloride, and extracted with ethyl acetate. The
extract was washed with three portions of water and
dried over anhydrous sodium sulfate, the solvent was
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chromatography on silica gel using toluene as eluent.
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equipped with a reflux condenser was charged with a
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corresponding substituted phthalonitrile, 0.13 mmol of
cobalt(II) chloride or zinc(II) acetate, 0.50 mmol of
DBU, and 5 ml of pentan-1-ol. The mixture was heated
to the boiling point (~138°C), kept for 2 h at that
temperature, cooled to room temperature, and treated
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pyridine, and the solution was subjected to
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concentrated under reduced pressure, the complex was
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(1:1), and the precipitate was washed on a filter with
hot ethanol and dried. The yields of phthalocyanines
X–XIV were about 40%.
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ACKNOWLEDGMENTS
19. McKeown, N.B., Li, H., and Madeleine, H., J.
Porphyrins Phthalocyanines, 2005, vol. 9, no. 12, p. 841.
This study was performed under financial support
by the Moscow Government.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008