4-acyloxy- and 4-acylaminophthalonitriles and phthalocyanines based thereon

Article abstract of DOI:10.1134/S1070428007110231

Reactions of 4-hydroxy- and 4-aminophthalonitriles with substituted benzoyl chlorides gave the corresponding N- and O-benzoyl derivatives, and the latter were used to obtain copper and nickel phthalocyanine complexes. Effect of the substituents in the latter on their electronic absorption spectra was studied. The obtained complexes were found to undergo association in organic solvents.

Full text of DOI:10.1134/S1070428007110231

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1719–1725. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © T.V. Tararykina, V.E. Maizlish, N.E. Galanin, G.P. Shaposhnikov, V.V.Bykova, N.V. Usol’tseva, 2007, published in Zhurnal
Organicheskoi Khimii, 2007, Vol. 43, No. 11, pp. 1718–1724.
4-Acyloxy- and 4-Acylaminophthalonitriles
and Phthalocyanines Based Thereon
T. V. Tararykinaa, V. E. Maizlisha, N. E. Galanina, G. P. Shaposhnikova,
V. V. Bykovab, and N. V. Usol’tsevab
a Ivanovo State University of Chemical Technology, pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
b Ivanovo State University, Ivanovo, Russia
Received November 19, 2006
Abstract—Reactions of 4-hydroxy- and 4-aminophthalonitriles with substituted benzoyl chlorides gave the
corresponding N- and O-benzoyl derivatives, and the latter were used to obtain copper and nickel phthalo-
cyanine complexes. Effect of the substituents in the latter on their electronic absorption spectra was studied.
The obtained complexes were found to undergo association in organic solvents.
DOI: 10.1134/S1070428007110231
Up to now, a large number of substituted phthalo-
cyanines were synthesized and studied. Introduction of
different substituents into the benzene rings of phthalo-
cyanine considerably affects physicochemical prop-
erties of this unique compound. An important place
among phthalocyanines is occupied by hydroxy- and
amino-substituted analogs and their derivatives such as
alkoxy, aroxy, etc. [1–4]. The presence of the above
substituents makes phthalocyanines soluble in organic
solvents and therefore extends the scope of their prac-
tical applications. The present work was aimed at syn-
thesizing new soluble phthalocyanines and their pre-
cursors, O- and N-benzoyl derivatives of 4-hydroxy-
and 4-aminophthalonitriles, and studying substituent
effects on the spectral parameters of phthalocyanine
metal complexes.
nitriles. Using 4-nitrophthalimide as starting com-
pound [5], we obtained 4-nitrophthalonitrile according
to the known procedure [6]. 4-Hydroxyphthalonitrile
(I) was synthesized by nucleophilic replacement of the
nitro group in 4-nitrophthalonitrile [7], and reduction
of the latter with tin(II) chloride in hydrochloric acid
gave 4-aminophthalonitrile (II) [8]. Compounds I and
II were then subjected to O- or N-acylation using
substituted benzoyl chlorides IIIa–IIIg which were
prepared in turn by treatment of the corresponding
benzoic acids with excess thionyl chloride (Scheme 1)
or phosphorus pentachloride (4-nitrobenzoic acid) [9].
It is known [9–11] that acylation with acid chlo-
rides is usually carried out in the presence of a base,
e.g., aqueous sodium hydroxide (Schotten–Bauman) or
an organic base such as pyridine (Einhorn reaction).
We used the second procedure where pyridine acted
simultaneously as solvent and catalyst. Pyridine with
acylating agents forms reactive species like N-ben-
zoylpyridinium, and it promotes partial ionization of
a hydroxy compound thus facilitating O-acylation.
Moreover, the use of pyridine as solvent prevents the
resulting esters and amides from undergoing hydrol-
ysis; therefore, the yield of the target products in-
creases. The reactions of nitriles I and II with benzoyl
chlorides IIIa–IIIg afforded esters IVa–IVg and
amides Va–Vg, respectively (Scheme 2). The products
were separated from unreacted hydroxy and amino
precursors by extraction into chloroform, followed by
In the first stage of our study we synthesized ben-
zoyl derivatives of 4-hydroxy- and 4-aminophthalo-
Scheme 1.
COOH
COCl
SOCl2 or PCl5
R
R
IIIa–IIIg
R = H (a), C9H19O (b), C10H21O (c), C11H23COO (d), 4-C7H15-
C6H4COO (e), 4-C8H17OC6H4COO (f), NO2 (g).
1719

TARARYKINA et al.
1720
Scheme 2.
R
NC
NC
OH
NC
O
IIIa–IIIg, pyridine
O
NC
I
IVa–IVg
R
H
N
NC
NC
NH2
NC
NC
IIIa–IIIg, pyridine
O
II
Va–Vg
R = H (a), C9H19O (b), C10H21O (c), C11H23COO (d), 4-C7H15C6H4COO (e), 4-C8H17OC6H4COO (f), NO2 (g).
removal of the solvent and extraction into acetone.
4-Nitrobenzoic acid derivatives IVg and Vg were
washed with diethyl ether to remove residual 4-nitro-
benzoic acid. Compounds IVa–IVg and Va–Vg are
yellowish crystalline substances or waxy materials that
are readily soluble in chloroform, acetone, and ben-
zene. They were identified on the basis of their ele-
mental compositions and spectral data (IR, 1H NMR,
and mass spectra).
at δ 1.29 ppm, the β-CH2 group gives rise to a multiplet
at δ 1.82 ppm, and the OCH2 signal is a triplet at
δ 4.05 ppm. The downfield region of the spectrum
contained multiplets at δ 6.92–7.80 and 7.81–8.15 ppm
corresponding to aromatic protons in the nonyloxy-
phenyl group and three protons of the phthalonitrile
fragment, respectively. Compound Va showed in the
mass spectrum the molecular ion peak with m/z 247
([M]+, Irel 100%) and ion peak with m/z 121 ([M – 126]+,
Irel 35%, PhCONH2).
The IR spectra of phthalonitriles IVa–IVg and Va–
Vg retained absorption bands due to stretching vibra-
tions of the cyano groups (2230–2240 cm–1), whereas
bands assignable to bending and stretching vibrations
of hydroxy group (1310–1320 cm–1) and primary
amino group (~3500, 1590–1650 cm–1) were absent.
All compounds displayed an absorption band in the
region 1670–1770 cm–1, which is typical of esters and
amides. The IR spectra of phthalodinitriles IV and
Vb–Vf contained absorption bands due to stretching
(2848–2930 cm–1) and asymmetric and symmetric
bending vibrations (1460–1480 and 1340–1391 cm–1)
of methyl and methylene C–H bonds. The secondary
amino group in compounds Va–Vg gave rise to
absorption at 3270–3350 cm–1, and vibrations of the
CAr–O–CAlk fragments in IVb, IVc, IVf, Vb, Vc, and
Vf were characterized by a frequency of 1250–
1257 cm–1. Nitro-substituted phthalonitriles also dis-
played absorption bands in the regions 1541–1566 and
1349–1351 cm–1 due to asymmetric and symmetric
stretching vibrations of the nitro group [12].
Copper phthalocyanine complexes VIa–VIg and
VIIa–VIIg were synthesized by reaction of the corre-
sponding substituted phthalonitriles IVa–IVg and Va–
Vg with copper(II) acetate, and nickel complexes
VIIIb, VIIIf, IXb, and IXf were obtained from nitriles
IVb, IVf, Vb, and Vf, respectively, and nickel(II)
acetate (Scheme 3). The reactions were carried out by
heating the reactants at 170–180°C. In the syntheses of
phthalocyanines VIg, VIIa, and VIIg, urea was added
to the reaction mixture. The products were isolated by
extraction into chloroform or dimethylformamide and
were purified by column chromatography on alumi-
num oxide. Complexes VI–IX are blue–green (acyloxy
derivatives) or green powders (acylamino derivatives)
that are soluble in DMF, chloroform, and benzene.
Exceptions are nitro-substituted derivatives VIg and
VIIg that are soluble only in DMF. Therefore, nitro
groups, regardless of their position in the molecule,
reduce the solubility in organic solvents.
The isolated metal phthalocyanine complexes were
1
1
In the H NMR spectrum of dinitrile IVb, signals
characterized by elemental analyses and IR, H NMR,
from protons in the alkoxy group appeared in the
upfield region. The triplet at δ 0.88 ppm belongs to
protons of the terminal methyl group, protons of the
six methylene groups resonate as a broadened singlet
and electronic absorption spectra. Their IR spectra con-
tained absorption bands at 1612–1624, 1505–1524,
1342–1360, 1246–1288, 1170–1188, 1140–1150, 1116–
1130, 1080–1092, 1048–1060, 910–950, 850–880, 770–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

4-ACYLOXY- AND 4-ACYLAMINOPHTHALONITRILES
1721
Scheme 3.
RC6H4COO
OCOC6H4R
N
M
N
N
N
N
N
M(OAc)2
N
IVa–IVg
N
RC6H4COO
OCOC6H4R
VIa–VIg, VIIIb, VIIIf
RC6H4CONH
NHCOC6H4R
N
N
N
N
N
M(OAc)2
M
N
N
Va–Vg
N
RC6H4CONH
NHCOC6H4R
VIIa–VIIg, IXb, IXf
VI, VII, M = Cu; VIII, IX, M = Ni.
780, and 734–736 cm–1, which are typical of phthalo-
cyanines [13]. In addition, absorption bands corre-
sponding to the acyl fragments were present (see the
IR spectra of the corresponding initial phthalonitriles,
given above).
the absorption band at λ 613–617 nm, indicating that
they tend to undergo association in solution [15]. As
might be expected, higher concentration of the mono-
meric form is observed in more polar solvents. The
presence of nitro groups induces a small red shift of
absorption bands in the electronic spectrum (cf. the
data for complexes VIg and VIa–VIf in table). The
electronic absorption spectra of N-acylamino-substi-
tuted copper complexes (see table) resemble those of
their acyloxy analogs. Only a slight red shift of the
long-wave Q-band may be noted for the former. The
nickel complexes are characterized by a small blue
shift of the absorption maxima as compared to the
corresponding copper complexes (see table).
1
The H NMR spectra of copper and nickel com-
plexes VIc and VIIIf are fairly similar. For example,
the following signals are present in the spectrum of
copper complex VIc, δ, ppm: 0.87 t (12H, CH3), 1.27 s
(56H, CH2), 1.78 m (8H, β-CH2), 4.03 t (8H, OCH2),
6.93 m (8H, m-H in RC6H4CO), 7.50–7.88 m (12H,
Harom), 8.10 m (8H, o-H in RC6H4CO).
In keeping with our previous data [14], the Q-band
in the electronic absorption spectra of acyloxy-substi-
tuted copper complexes is located at a longer wave-
length than in the spectra of copper phthalocyanine; on
the other hand, it is displaced by 13–15 nm toward
shorter wavelengths, as compared to (tetra-4-hydroxy-
phthalocyaninato)copper(II). This results from reduc-
tion of the electron-donor power of the hydroxy group
owing to acylation. An analogous pattern is observed
for the N-acylated complexes. Acyloxy-substituted
phthalocyanine complexes VIa–VIg in chloroform and
DMF are characterized by relatively high intensity of
EXPERIMENTAL
The electronic absorption spectra were measured on
a Hitachi U-2001 spectrophotometer. The IR spectra
were recorded in the frequency region from 400 to
4000 cm–1 on an Avatar 360 FT-IR spectrometer from
samples prepared as KBr pellets. The 1H NMR spectra
were obtained on a Bruker AMD-200 instrument from
solutions in CDCl3. The mass spectra were run on
a Varian Saturn 2000K mass spectrometer. The ele-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

TARARYKINA et al.
Electronic absorption spectra of copper and nickel phthalocyanine complexes VI–IX
1722
λ
max, nm (D/Dmax)
Compound no.
R
DMF
CHCl3
H
671 (1.00), 610 (0.63)
670 (1.00), 617 (0.74)
610, 671 (1.00/ 1.65)
690 (1.00), 621 (0.45)
671 (1.00), 618 (0.72)
670 (1.00), 616 (0.85)
689 (1.00), 625 (0.69)
690 (1.00), 626 (0.41)
692 (1.00) 626 (0.86)
692 (1.00), 638 (0.72)
690 (1.00), 621 (0.53)
700 (0.90), 643 (1.00)
690 (1.00) 627 (0.52)
693 (1.00), 627 (0.74)
666 (1.00), 622 (0.70)
664 (1.00), 613 (0.97)
686 (1.00), 625 (0.71)
687 (1.00), 639 (0.86)
672 (1.00), 616 (0.75)
671 611, (1.00/ 1.26)
672 (1.00), 613 (0.79)
672 (1.00), 616 (0.51)
672 (1.00), 614 (0.96)
672 (1.00), 617 (0.93)
VIa
C9H19O
C10H21O
VIb
VIc
C11H23COO
4-C7H15C6H4COO
4-C8H17OC6H4COO
NO2
VId
VIe
VIf
VIg
H
VIIa
VIIb
VIIc
VIId
VIIe
VIIf
VIIg
VIIIb
VIIIf
IXb
IXf
C9H19O
624
C10H21O
625
C11H23COO
4-C7H15C6H4COO
4-C8H17OC6H4COO
NO2
695 (0.60), 616 (1.00)
696 (0.70), 615 (1.00)
692 (1.00), 644 (0.97)
C9H19O
665 (1.00), 631 (0.76)
4-C8H17OC6H4COO
C9H19O
664 (1.00), 622 (0.82)
625
626
4-C8H17OC6H4COO
mental compositions were determined using a FlashEA H 4.8; N 11.8. C15H8N2O2. Calculated, %: C 72.5;
1112 CHNS–O analyzer.
H 3.3; N 11.3.
4-Benzoylamino- and 4-benzoyloxyphthalo-
nitriles IVa–IVf and Va–Vf (general procedure).
A mixture of 0.01 mmol of benzoic or substituted ben-
zoic acid and 0.14 ml (2 mmol) of thionyl chloride was
heated under stirring to 40–50°C and was kept at that
temperature until hydrogen chloride no longer evolved.
Excess thionyl chloride was distilled off, 0.14 g
(1 mmol) of dinitrile I or 0.14 g (1.1 mmol) of dinitrile
II and 3 ml of pyridine were added to the residue, and
the mixture was heated to 80°C and kept for 16 h at
that temperature. The mixture was poured into water,
and the viscous material was filtered off, dried at 50°C
under reduced pressure, and dissolved in 10 ml of
chloroform. The solution was filtered, the filtrate was
evaporated, the residue was dissolved in 10 ml of
acetone, the solution was filtered, and the filtrate was
evaporated.
3,4-Dicyanophenyl 4-(nonyloxy)benzoate (IVb)
was obtained from 0.28 g of 4-(nonyloxy)benzoic acid.
Yield 0.32 g (82%), off-white powder. IR spectrum, ν,
cm–1: 2235 (C≡N); 1735 (C=O); 2920, 2852 (C–H);
1
1257 (C–O–C). H NMR spectrum, δ, ppm: 0.88 t
(3H), 1.29 s (12H), 1.82 m (2H), 4.05 t (2H), 6.92–
7.80 m (4H), 7.81–8.15 m (3H). Found, %: C 73.3;
H 6.9; N 7.0. C24H26N2O3. Calculated, %: C 73.8;
H 6.7; N 7.2.
3,4-Dicyanophenyl 4-(decyloxy)benzoate (IVc)
was obtained from 0.26 g of 4-(decyloxy)benzoic acid.
Yield 0.33 g (83%), off-white powder. IR spectrum, ν,
cm–1: 2235 (C≡N); 1739 (C=O); 2920, 2851 (C–H);
1257 (C–O–C). Found, %: C 73.9; H 7.3; N 6.7.
C25H28N2O3. Calculated, %: C 74.2; H 7.0; N 6.9.
3,4-Dicyanophenyl 4-(dodecanoyloxy)benzoate
(IVd) was obtained from 0.32 g of 4-(dodecanoyloxy)-
benzoic acid. Yield 0.39 g (87%), off-white powder. IR
spectrum, ν, cm–1: 2242 (C≡N); 1743, 1760 (C=O);
2919, 2849 (C–H). Found, %: C 72.4; H 7.1; N 6.0.
C27H30N2O4. Calculated, %: C 72.6; H 6.8; N 6.3.
3,4-Dicyanophenyl benzoate (IVa) was obtained
from 0.12 g of benzoic acid. Yield 0.21 g (84%), white
powder, mp 130–132°C. IR spectrum, ν, cm–1: 2234
(C≡N), 1745 (C=O). 1H NMR spectrum, δ, ppm: 7.22–
7.56 m (5H), 7.92–8.12 m (3H). Found, %: C 72.3;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

4-ACYLOXY- AND 4-ACYLAMINOPHTHALONITRILES
1723
2853 (C–H). Found, %: C 74.6; H 6.0; N 8.7.
C29H27N3O3. Calculated, %: C 74.8; H 5.9; N 9.0.
3,4-Dicyanophenyl 4-(4-heptylbenzoyloxy)ben-
zoate (IVe) was obtained from 0.34 g of 4-(4-heptyl-
benzoyloxy)benzoic acid. Yield 0.40 g (86%), off-
white waxy material. IR spectrum, ν, cm–1: 2235
(C≡N); 1735 br (C=O); 2924, 2853 (C–H). Found, %:
C 74.5; H 6.0; N 5.8. C29H26N2O4. Calculated, %:
C 74.7; H 5.6; N 6.0.
4-(3,4-Dicyanophenylcarbamoyl)phenyl 4-(octyl-
oxy)benzoate (Vf) was obtained from 0.37 g of
4-[4-(octyloxy)benzoyloxy]benzoic acid. Yield 0.41 g
(81%), yellow waxy substance. IR spectrum, ν, cm–1:
2236 (C≡N); 1720 br (C=O); 1689, 3339 (N–H); 2930,
2857 (C–H); 1257 (C–O–C). Found, %: C 71.3; H 8.0;
N 8.5. C30H37N3O4. Calculated, %: C 71.5; H 7.4;
N 8.3.
3,4-Dicyanophenyl 4-[4-(octyloxy)benzoyloxy]-
benzoate (IVf) was obtained from 0.37 g of 4-[4-(oc-
tyloxy)benzoyloxy]benzoic acid. Yield 0.43 g (86%),
off-white waxy material. IR spectrum, ν, cm–1: 2235
(C≡N); 1689, 1738 (C=O); 2935, 2857 br (C–H); 1259
4-(3,4-Dicyanophenyl) 4-nitrobenzoate (IVg).
A mixture of 0.19 g (1 mmol) of 4-nitrobenzoyl
chloride, 0.14 g of dinitrile I, and 3 ml of pyridine was
heated for 16 h at 80°C. The mixture was poured into
water, the precipitate was filtered off, dried at 70°C
under reduced pressure, washed with diethyl ether to
remove p-nitrobenzoic acid, and extracted with chloro-
form, and the extract was evaporated. Yield 0.17 g
(61%), white powder. IR spectrum, ν, cm–1: 2242
(C≡N); 1693 (C=O); 1349, 1566 (NO2). Found, %:
C 61.2; H 2.7; N 14.0. C15H7N3O4. Calculated, %:
C 61.4; H 2.4; N 14.3.
1
(C–O–C). H NMR spectrum, δ, ppm: 0.87 t (3H),
1.26 s (10H), 1.85 m (2H), 4.09 t (2H), 6.88–7.12 m
(4H), 7.15–7.33 m (4H), 7.88–8.33 m (3H). Found, %:
C 71.0; H 7.5; N 5.3. C30H36N2O5. Calculated: C 71.4;
H 7.2; N 5.6.
N-(3,4-Dicyanophenyl)benzamide (Va) was ob-
tained from 0.12 g of benzoic acid. Yield 0.21 g (84%),
off-white powder, mp 169–171°C. IR spectrum, ν,
cm–1: 2214 (C≡N); 1692 (C=O); 1600, 3344 (N–H).
Found, %: C 72.7; H 4.0; N 16.7. C15H9N3O. Calculat-
ed: C 72.9; H 3.7; N 17.0.
N-(3,4-Dicyanophenyl)-4-nitrobenzamide (Vg).
A mixture of 0.19 g (1 mmol) of 4-nitrobenzoyl
chloride, 0.14 g of dinitrile II, and 3 ml of pyridine
was heated for 16 h at 80°C. The mixture was poured
into water, the precipitate was filtered off, dried at
70°C under reduced pressure, washed with diethyl
ether to remove p-nitrobenzoic acid, and extracted with
chloroform, and the extract was evaporated. Yield
0.18 g (64%), yellow powder. IR spectrum, ν, cm–1:
2214 (C≡N); 1693 (C=O); 1693, 3350 (N–H); 1351,
1541 (NO2). Found, %: C 61.4; H 3.0; N 19.0.
C15H8N4O3. Calculated, %: C 61.7; H 2.8; N 19.2.
N-(3,4-Dicyanophenyl)-4-(nonyloxy)benzamide
(Vb) was obtained from 0.26 g of 4-(nonyloxy)benzoic
acid. Yield 0.32 g (81%), off-white powder. IR spec-
trum, ν, cm–1: 2239 (C≡N); 1769 (C=O); 1670, 3344
(N–H); 2921, 2852 (C–H); 1251 (C–O–C). Found, %:
C 73.6; H 7.3; N 10.6. C24H27N3O2. Calculated, %:
C 74.0; H 7.0; N 10.8.
4-Decyloxy-N-(3,4-dicyanophenyl)benzamide
(Vc) was obtained from 0.28 g of 4-(decyloxy)benzoic
acid. Yield 0.32 g (80%), off-white powder. IR spec-
trum, ν, cm–1: 2239 (C≡N); 1765 (C=O); 1670, 3344
(N–H); 2920, 2851 (C–H); 1253 (C–O–C). Found, %:
C 74.2; H 7.5; N 10.2. C25H29N3O2. Calculated, %:
C 74.4; H 7.2; N 10.4.
Tetra[benzoyloxy(amino)]phthalocyanine copper
and zinc complexes VI–IX (gemeral procedure).
A mixture of 1 mmol of the corresponding phthalo-
dinitrile IV or V and 0.06 g (0.3 mmol) of copper(II)
acetate or 0.08 g (0.3 mmol) of nickel(II) acetate was
heated for 1.5 h at 170–180°C. The mixture was ex-
tracted with chloroform, and the extract was subjected
to column chromatography on aluminum oxide
(Brockmann activity grade II) using chloroform–
methanol (4:1 by volume) as eluent (complex VIIa
was isolated using DMF as eluent). Compounds VIg
and VIIg were purified by extraction with acetone and
methanol to remove impurities.
4-(3,4-Dicyanophenylcarbamoyl)phenyl dodeca-
noate (Vd) was obtained from 0.32 g of 4-(dodeca-
noyloxy)benzoic acid. Yield 0.36 g (80%), yellow
powder. IR spectrum, ν, cm–1: 2231 (C≡N); 1755 br
(C=O); 1702, 3343 (N–H); 2921, 2849 (C–H). Found,
%: C 72.5; H 7.7; N 9.2. C27H31N3O3. Calculated:
C 72.8; H 7.0; N 9.4.
4-(3,4-Dicyanophenylcarbamoyl)phenyl 4-hep-
tylbenzoate (Ve) was obtained from 0.34 g of
4-(4-heptylbenzoyloxy)benzoic acid. Yield 0.40 g
(86 %), yellow waxy substance. IR spectrum, ν, cm–1:
2214 (C≡N); 1735 br (C=O); 1689, 3343 (N–H); 2924,
[2,9(10),16(17),23(24)-Tetra(benzoyloxy)phthalo-
cyaninato]copper(II) (VIa) was obtained from 0.25 g
of compound IVa. Yield 0.25 g (24%), blue–green
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

TARARYKINA et al.
1724
powder. IR spectrum: ν 1745 cm–1 (C=O). Found, %:
C 67.9; H 3.5; N 10.3. C60H32CuN8O8. Calculated, %:
C 68.2; H 3.1; N 10.6.
of urea. Yield 0.25 g (24%), green powder. IR spec-
trum, ν, cm–1: 1692 (C=O); 1600, 3344 (N–H). Found,
%: C 68.2; H 4.0; N 15.6. C60H36CuN12O4. Calculated,
%: C 68.5; H 3.5; N 16.0.
{2,9(10),16(17),23(24)-Tetrakis[4-(nonyloxy)-
benzoyloxy]phthalocyaninato}copper(II) (VIb) was
obtained from 0.39 g of compound IVb. Yield 0.24 g
(20%), blue–green powder. IR spectrum, ν, cm–1: 1735
(C=O); 2920, 2852 (C–H); 1257 (C–O–C). Found, %:
C 70.5; H 6.7; N 6.5. C96H104CuN8O12. Calculated, %:
C 70.9; H 6.5; N 6.9.
{2,9(10),16(17),23(24)-Tetrakis[4-(nonyloxy)ben-
zoylamino]phthalocyaninato}copper(II) (VIIb) was
obtained from 0.39 g of compound Vb. Yield 0.38 g
(25%), green powder. IR spectrum, ν, cm–1: 1769
(C=O); 1670, 3344 (N–H); 2921, 2852 (C–H); 1251
(C–O–C). Found, %: C 71.0; H 7.0; N 10.1.
C96H108CuN12O8. Calculated, %: C 71.1; H 6.7; N 10.4.
{2,9(10),16(17),23(24)-Tetrakis[4-(decyloxy)-
benzoyloxy]phthalocyaninato}copper(II) (VIc) was
obtained from 0.41 g of compound IVc. Yield 0.31 g
(19%), blue–green powder. IR spectrum, ν, cm–1: 1739
{2,9(10),16(17),23(24)-Tetrakis[4-(decyloxy)ben-
zoylamino]phthalocyaninato}copper(II) (VIIc) was
obtained from 0.39 g of compound Vc. Yield 0.33 g
(20%), green powder. IR spectrum, ν, cm–1: 1765
(C=O); 1670, 3344 (N–H); 2920, 2851 (C–H); 1253
(C–O–C). Found, %: C 74.1; H 7.5; N 10.1.
C100H116CuN12O8. Calculated, %: C 74.4; H 7.2; N 10.4.
1
(C=O); 2920, 2851 (C–H); 1257 (C–O–C). H NMR
spectrum, δ, ppm: 0.87 t (12H), 1.27 s (56H), 1.78 m
(8H), 4.03 t (8H), 6.93 m (8H), 7.50–7.88 m (12H),
8.10 m (8H). Found, %: C 74.0; H 7.2; N 6.6.
C100H112CuN8O12. Calculated, %: C 74.2; H 7.0; N 6.9.
{2,9(10),16(17),23(24)-Tetrakis[4-(dodecanoyl-
oxy)benzoylamino]phthalocyaninato}copper(II)
(VIId) was obtained from 0.45 g of compound Vd.
Yield 0.40 g (22%), green powder. IR spectrum, ν, cm–1:
1755 br (C=O); 1702, 3343 (N–H); 2921, 2849 (C–H).
Found, %: C 70.0; H 7.0; N 8.8. C108H124CuN12O12.
Calculated, %: C 70.3; H 6.8; N 9.1.
{2,9(10),16(17),23(24)-Tetrakis[4-(dodecanoyl-
oxy)benzoyloxy]phthalocyaninato}copper(II) (VId)
was obtained from 0.45 g of compound IVd. Yield
0.40 g (22%), blue–green powder. IR spectrum, ν,
cm–1: 1743, 1760 (C=O); 2919, 2849 (C–H). Found,
%: C 70.0; H 6.2; N 6.0. C108H120CuN8O16. Calculated,
%: C 70.1; H 6.1; N 6.5.
{2,9(10),16(17),23(24)-Tetrakis[4-(4-heptylben-
zoyloxy)benzoylamino]phthalocyaninato}copper(II)
(VIIe) was obtained from 0.47 g of compound Ve.
Yield 0.41 g (21%), green powder. IR spectrum, ν, cm–1:
1735 br (C=O); 1689, 3343 (N–H); 2924, 2853 (C–H).
Found, %: C 72.0; H 6.0; N 9.0. C116H108N12CuO12.
Calculated, %: C 72.4; H 5.7; N 8.7.
{2,9(10),16(17),23(24)-Tetrakis[4-(4-heptylben-
zoyloxy)benzoyloxy]phthalocyaninato}copper(II)
(VIe) was obtained from 0.47 g of compound IVe.
Yield 0.43 g (22%), blue–green powder. IR spectrum,
ν, cm–1: 1735 br (C=O); 2924, 2853 (C–H). Found, %:
C 72.0; H 5.6; N 5.5. C116H104CuN8O16. Calculated, %:
C 72.2; H 5.3; N 5.8.
[2,9(10),16(17),23(24)-Tetrakis{4-[4-(octyloxy)-
benzoyloxy]benzoylamino}phthalocyaninato]cop-
per(II) (VIIf) was obtained from 0.50 g of compound
Vf. Yield 0.42 g (21%), green powder. IR spectrum, ν,
cm–1: 1720 br (C=O); 1689, 3339 (N–H); 2930, 2857
(C–H); 1257 (C–O–C). Found, %: C 70.2; H 5.9; N 8.0.
C120H116N12CuO16. Calculated, %: C 70.5; H 5.7; N 8.2.
[2,9(10),16(17),23(24)-Tetrakis{4-[4-(octyloxy)-
benzoyloxy]benzoyloxy}phthalocyaninato]cop-
per(II) (VIf) was obtained from 0.50 g of compound
IVf. Yield 0.50 g (25%), blue–green powder. IR spec-
trum, ν, cm–1: 1689, 1738 (C=O); 2922, 2851 br (C–H);
1258 (C–O–C). Found, %: C 70.6; H 5.7; N 5.2.
C120H112CuN8O20. Calculated, %: C 70.3; H 5.5; N 5.5.
[2,9(10),16(17),23(24)-Tetra(4-nitrobenzoyl-
amino)phthalocyaninato]copper(II) (VIIg) was ob-
tained from 0.29 g of compound Vg. Yield 0.25 g
(21%), green powder. IR spectrum, ν, cm–1: 1693
(C=O); 1693, 3350 (N–H); 1351, 1541 (NO2). Found,
%: C 61.0; H 2.9 N 14.0. C60H32CuN12O12. Calculated,
%: C 61.3; H 2.7; N 14.3.
[2,9(10),16(17),23(24)-Tetra(4-nitrobenzoyloxy)-
phthalocyaninato]copper(II) (VIg) was obtained
from 0.29 g of compound IVg. Yield 0.24 g (21%),
blue–green powder. IR spectrum, ν, cm–1: 1693 (C=O);
1349, 1566 (NO2). Found, %: C 60.8; H 2.7; N 9.2.
C60H28CuN8O16. Calculated, %: C 61.0; H 2.4; N 9.5.
[2,9(10),16(17),23(24)-Tetra(benzoylamino)-
phthalocyaninato]copper(II) (VIIa) was obtained
from 0.25 g of compound Va in the presence of 0.2 g
{2,9(10),16(17),23(24)-Tetrakis[4-(nonyloxy)ben-
zoyloxy]phthalocyaninato}nickel(II) (VIIIb) was
obtained from 0.39 g of compound IVb. Yield 0.32 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

4-ACYLOXY- AND 4-ACYLAMINOPHTHALONITRILES
1725
(20%), blue–green powder. IR spectrum, ν, cm–1: 1735
(C=O); 2920, 2852 (C–H); 1257 (C–O–C). Found, %:
C 70.9; H 7.1; N 6.7. C96H104N8NiO12. Calculated, %:
C 71.2; H 6.9; N 6.9.
2. Leznoff, C.C., D’Ascanio, A.M., and Yildiz, S.Z.,
J. Porphyrins Phthalocyanines, 2000, vol. 4, p. 103.
3. Maizlish, V.E., Balakirev, A.E., Shishkina, O.V., and
Shaposhnikov, G.P., Russ. J. Gen. Chem., 2001, vol. 71,
p. 246.
[2,9(10),16(17),23(24)-Tetrakis{4-[4-(octyloxy)-
benzoyloxy]benzoyloxy}phthalocyaninato]nickel(II)
(VIIIf) was obtained from 0.50 g of compound IVf.
Yield 0.46 g (23%), blue–green powder. IR spectrum,
ν, cm–1: 1689, 1738 (C=O); 2922, 2851 br (C–H);
4. Maizlish, V.E., Shaposhnikov, G.P., Bykova, V.V., and
Usol’tseva, N.V., Russ. J. Gen. Chem., 2002, vol. 72,
p. 1636.
5. Rodionov, V.M., Bogoslovskii, B.M., and Fedoro-
va, A.M., Laboratornoe rukovodstvo po khimii prome-
zhutochnykh produktov i krasitelei (Laboratory Manual
on the Chemistry of Intermediate Products and Dyes),
Moscow: NTKhim, 1948.
1
1258 (C–O–C). H NMR spectrum, δ, ppm: 0.82 t
(12H), 1.28 s (40H), 1.86 m (8H), 4.11 t (8H), 6.77–
7.05 m (16H), 7.18–7.39 m (16H), 7.99–8.56 m (12H).
Found, %: C 70.3; H 5.8; N 5.2. C120H112N8NiO20. Cal-
culated, %: C 70.5; H 5.5; N 5.5.
6. Thiel, W. and Mayer, R., J. Prakt. Chem., 1986,
vol. 328, p. 497.
7. Ustinov, V.D., Plakhtinskii, V.V., Mironov, T.S., and
Ryabukhina, N.S., Zh. Org. Khim., 1979, vol. 15,
p. 1775.
{2,9(10),16(17),23(24)-Tetrakis[4-(nonyloxy)ben-
zoylamino]phthalocyaninato}nickel(II) (IXb) was
obtained from 0.39 g of compound Vb. Yield 0.33 g
(20%), green powder. IR spectrum, ν, cm–1: 1769
(C=O); 1670, 3344 (N–H); 2921, 2852 (C–H); 1251
(C–O–C). Found, %: C 71.0; H 7.1; N 10.1.
C96H108N12NiO8. Calculated, %: C 71.3; H 6.7; N 10.4.
8. Islyaikin, M.K., Cand. Sci. (Chem.) Dissertation,
Ivanovo, 1980.
9. Tietze, L.-F. and Eicher, T., Reactions and Syntheses
in the Organic Chemistry Laboratory, Mill Valley,
California: University Science Books, 1989.
10. Lisitsyn, V.N., Khimiya i tekhnologiya promezhutoch-
nykh produktov. Uchebnik dlya VUZov (Chemistry and
Technology of Intermediate Products. Textbook for
Higher Education Institutions), Moscow: Khimiya,
1987.
11. Weygand–Hilgetag Organisch-chemische Experimen-
tierkunst, Hilgetag, G. and Martini, A., Eds., Leipzig:
Johann Ambrosius Barth, 1964, 3rd ed.
[2,9(10),16(17),23(24)-Tetrakis{4-[4-(octyloxy)-
benzoyloxy]benzoylamino}phthalocyaninato]nick-
el(II) (IXf) was obtained from 0.50 g of compound Vf.
Yield 0.43 g (21%), green powder. IR spectrum, ν,
cm–1: 1720 br (C=O); 1689, 3339 (N–H); 2930, 2857
(C–H); 1257 (C–O–C). Found, %: C 70.3; H 6.0 N 8.0.
C120H116N12NiO16. Calculated, %: C 70.6; H 5.7; N 8.2.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. RNP.2.2.1.1.7280) and
by the Russian Foundation for Basic Research (project
no. 04-03-32305).
12. Dyer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, Englewood Cliffs: Prentice–Hall,
1965.
13. Sidorov, A.R. and Kotlyar, I.P., Optika Spektrosk., 1961,
vol. 11, p. 175.
14. Maizlish, V.E., Shaposhnikov, G.P., Snegireva, F.P., Mo-
chalova, N.L., and Smirnov, R.P., Izv. Vyssh. Uchebn.
Zaved., Ser. Khim. Khim. Tekhnol., 1988, vol. 31, p. 42.
REFERENCES
1. Balakirev, A.E., Maizlish, V.E., Shaposhnikov, G.P., and
15. Monahan, A.R., Brado, J.A., and DeLuca, A.F., J. Phys.
Chem., 1972, vol. 76, p. 446.
Smirnov, R.P., Russ. J. Gen. Chem., 2000, vol. 70, p. 623.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007