Synthesis and properties of tetra-4-morpholinyl(piperidinyl)-5-R- substituted phthalocyanines

Article abstract of DOI:10.1134/S1070363213040257

Demetallation of magnesium tetra-4-morpholinyl(piperidinyl)-5-R-substituted phthalocyanines was performed to obtain the corresponding metal-free phthalocyanines. Their electronic absorption spectra were shown to depend on the nature of the solvent. It was

Full text of DOI:10.1134/S1070363213040257

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 4, pp. 757–761. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.I. Fedotova, Yu.M. Zhuravleva, V.E. Maizlish, G.P. Shaposhnikov, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 4, pp. 675–680.
Synthesis and Properties
of Tetra-4-morpholinyl(piperidinyl)-5-R-Substituted
Phthalocyanines
A. I. Fedotova, Yu. M. Zhuravleva, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemical Technology, pr. F. Engel’sa 7, Ivanovo, 153000 Russia
е-mail: ttoc@isuct.ru
Received March 23, 2012
Abstract—Demetallation of magnesium tetra-4-morpholinyl(piperidinyl)-5-R-substituted phthalocyanines was
performed to obtain the corresponding metal-free phthalocyanines. Their electronic absorption spectra were
shown to depend on the nature of the solvent. It was found that both the saturated heterocycle and the oxyaryl
substituent have almost no effect on the position of the absorption maximum.
DOI: 10.1134/S1070363213040257
Phthalocyanines (Рс) and related compounds have
attracted the attention of researchers for already more
than seven decades in view of their unique physico-
chemical properties which are closely associated with
their peculiar molecular structure [1–11].
rings [1–5]. The introduction of substituents in Pc
allows wide variation of their physicochemical
properties (solubility in various solvents, thermal stability,
catalytic, liquid-crystalline, coloristic properties, etc.).
Proceeding with systematic research in the
chemistry of phthalocyanines and related compounds
[4, 5, 12–20], in the present work we synthesized
As known, one of the ways of chemical
modification of Рс is functional substitution in benzene
R
Het
N
N
N
N
Het
R
Het
R
NC
NC
NH
N
HN
R
Het
N
R
Het
I−V
(b);
Het =
O
N
O (а),
N
R =
(Iа, Ib),
O
CH3
(IIа, IIb),
O
CH3
(Vb).
(IIIа),
O
Cl (IVа),
CH3
S
757

758
FEDOTOVA et al.
electronic absorption spectra of the target products no
D
longer contain the Q band characteristics of the
magnesium complexes and show two bands typical of
ligands (Fig. 1). The splitting of the Q band of H2Pc
into two components is due to the D2h symmetry of
these molecules [3].
The resulting ligands were identified by elemental
analysis and electronic, 1Н NMR, and IR spectroscopy.
The IR spectra showed absorption bands characteristic
of phthalocyanine compounds [21, 22]. In the range
2840–2930 cm–1 there are absorption bands of methyl
and methylene С–Н bonds of saturated monoaza
cycles and alkyl fragments of phthalocyanines. The
spectra of compounds I–IV containing aryloxy groups
show bands at 1210–1220 cm–1, which are assignable
to Аr–О–Аr vibrations. The band at 1128 cm–1 in the
spectrum of compound Vb corresponds to Ar–S–Ar
vibrations [23]. At 3285–3324 and 1007–1010 cm–1
absorption bands characteristic of metal-free phthalo-
cyanines are observed [21, 24]. It was found that the
nature of the saturated heterocycle has no effect on the
shape and position of bands in the IR spectra.
λmax, nm
Fig. 1. Electron absorption spectra in chloroform:
(1) magnesium tetra-4-(morpholin-4-yl)tetra-5-phenoxy-
phthalocyanine and (2) tetra-4-(morpholin-4-yl)tetra-5-
phenoxyphthalocyanine (Ia).
metal-free morpholine- and piperidine-substituted
phthalocyanines and studied some of their
physicochemical properties.
The 1Н NMR spectra of phthalocyanines are similar
to the spectra of the corresponding phthalonitriles [25].
Furthermore, in our case an upfield signal from
endocyclic NH protons (from –2.00 to –2.02 ppm) is
observed which is absent from the spectrum of the
parent metal complex (Fig. 2).
There has been some information in the literature
on the synthesis of metal-free phthalocyanines with
heterocyclic substituents by fusing the corresponding
phthalonitriles (method а) [20]. It was also experi-
mentally established that some metal-free phthalo-
cyanines [Н2Рс(4-Het)4(5-R)4] can be prepared by
heating the starting phtnalonitriles but in quite low
yields which slightly increase in the presence of urea
(Table 1, method b). Therefore, compounds I–V were
prepared by demetallation of the corresponding
magnesium complexes by their reprecipitation from
glacial acetic acid solutions (method c). The reaction
progress was followed by spectrophotometry. The
The synthesized compounds are soluble in organic
solvents (DMF, DMSO, chloroform, etc.) and
concentrated sulfuric acid. Moreover, the presence of
the morpholine and piperidine fragments endow these
compounds with solubility in concentrated hydro-
chloric acid and glacial acetic acid.
Analysis of the electronic absorption spectra
showed that they are solvent dependent (Figs. 3 and 4;
Tables 2 and 3). In DMF, the ligands are present as
associates. The spectra of these compounds in the
visible region (636–709 nm) contain an absorption
band which is broadened or split in two components.
The shape of the spectrum depends on the
concentration of the phthalocyanine. Upon strong
dilution (to <10–7 М), the spectrum transforms into a
one-band spectrum (Fig. 3) which is quite similar to
the spectra of metal complexes; the same phenomenon
was previously obtained with other substituted metal-
free phthalocyanines and was explained by the
formation of a dianion with D4h symmetry [22]. In
other organic solvents (except for DMSO) the
Table 1. Conditions of synthesis of metal-free phthalo-
cyanines I–V
Yield, %
Comp. no.
method а
method b
method c
–
–
22
–
58
47
55
58
41
57
48
Ia
Ib
9
19
–
IIa
IIb
IIIa
IVa
Vb
–
9
24
15
32
10
12
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

SYNTHESIS AND PROPERTIES OF TETRA-4-MORPHOLINYL(PIPERIDINYL)-...
759
(a)
(b)
3
8
6
9.0 8.0 7.0
4.0 3.0 2.0 1.0 0.0 –1.0 –2.0
5
δ, ppm
2
4
7
5
4
2
3
1
1
δ, ppm
Fig. 2. 1Н NMR spectra of (a) 1-tetra-4-(morpholin-4-yl)tetra-5-phenoxyphthalocyanine (Ia) and (b) nickel 2-tetra-4-(morpholin-4-
yl)tetra-5-phenoxyphthalocyanine.
spectrum is typical of the ligands. The spectrum of
compound IIIa in the visible region contains two
absorption bands (Q1 and Q2) at 714–719 and 684–695
nm (Fig. 4, Tables 2 and 3), and, therewith, the
intensity ratio of the Q1 and Q2 bands and their
positions are solvent-dependent (Fig. 4, Table 3). The
electronic absorption spectrum in DMSO contains one
absorption band, thus providing evidence showing that,
like in DMF, the compound is present in the dianionic
form (Table 3). In was found that the nature of both the
oxyaryl fragment and the saturated heterocycle
scarcely affects the position of the absorption
maximum (Table 2).
The replacement of the “bridging” oxygen atoms of
the phenoxy groups of tetra-4-(piperidin-1-yl)tetra-5-
phenoxyphthalocyanine (Ib) by the sulfur atom to
obtain tetra-4-(piperidin-1-yl)tetra-5-phenylsulfanyl-
phthalocyanine (Vb) leads to a red shift of the long-
wave band by 10–11 nm (Table 2), which was pre-
viously observed with other substituted phthalo-
cyanines [14].
Q2 Q1
D
D
λ, nm
λ, nm
Fig. 3. Electron absorption spectra of tetra-4-(morpholin-4-
yl)tetra-5-(2'-naphthyloxy)phthalocyanine (IIIa) in DMF:
(1) c 10–5 М and (2) c 10–7 М.
Fig. 4. Electron absorption spectra of tetra-4-(morpholin-4-
yl)tetra-5-(2'-naphthyloxy)phthalocyanine (IIIa) in (1)
pyridine, (2) dioxane. (3) chloroform, and (4) DMF (c 10–5 М).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

760
FEDOTOVA et al.
Table 2. Long-wave absorption maxima of phthalocyanines
I–V
Table 3. Intensity ratios of the Q2 and Q1 bands in the elec-
tron absorption spectra of tetra-4-(morpholin-4-yl)tetra-5-
(2'-naphthyloxy)phthalocyanine (IIIa)
λ
max, nm (log ε)
Compound
λmax, nm
CHCl3
DMF
693
Solvent
D(Q2)/D(Q1)
Q1
Q2
717 (5.17), 685 (5.14)
717 (5.02), 685 (4.99)
718 (5.02), 687 (4.98)
720 (4.99), 687 (4.96)
720 (4.98), 688 (4.95)
719 (4.98), 687 (4.93)
727 (5.16), 696 (5.13)
Ia
Chloroform
Benzene
Toluene
Dioxane
THF
717
719
719
714
716
718
719
–
688
688
688
687
687
684
695
686
0.87
0.91
0.93
1.00
0.95
1.01
1.10
7.00
693
691
691
692
694
703
Ib
IIa
IIb
IIIа
IVа
Vb
CCl4
Pyridine
DMSO
from 76 mg of 4-(morpholin-4-yl)tetra-5-phenoxy-
phthalonitrile. Yield 44 mg (58%). IR spectrum, ν, cm–1:
3285, 1007 (NH), 2869, 2833 (CH2), 1208 (Ar–O–Ar).
1H NMR spectrum, δ, ppm: 7.96 s (4H, Н3), 7.55 m
(8H, H7), 7.43 s (4H, Н8), 7.08 s (4H, H2), 6.92 m (8H,
H6), 3.65 m (16H, H5), 3.30 m (16H, H4), –2.00 m (2H,
H1). Found, %: С 70.50; Н 5.21; N 13.31. С72H62N12O8.
Calculated, %: С 70.69; Н 5.11; N 13.74.
EXPERIMENTAL
The electron absorption spectra were registered in
organic solvents on a Perkin Elmer Lambda 200 UV/
Vis spectrophotometer at room temperature in the
range 325–900 nm. The IR spectra were measured on
an Avatar 360 ESP FT–IR spectrometer in the range
400–4000 cm–1 in thin films (chloroform). The Н
1
NMR spectra were obtained on a Bruker DRX-500
spectrometer in 5% solutions in CDCl3 against internal
TMS. The elemental analysis was performed on a
FlashEA 1112 CHNS/O instrument.
Tetra-4-(morpholin-4-yl)tetra-5-{[3,4'-dimethyl-
(1,1'-biphenyl)-4-yl]oxy}phthalocyanine (IIa) was
obtained by the general procedure from 102 mg of 4-
(morpholin-4-yl)tetra-5-{[3,4'-dimethyl(1,1'-biphenyl)-
4-yl]oxy}phthalonitrile. Yield 49 mg (48%). IR spec-
trum, ν, cm–1: 3295, 1005 (NH), 2870, 2832 (CH2),
1208 (Ar–O–Ar). Found, %: С 76.01; Н 5.98; N 10.04.
С104H92N12O8. Calculated, %: С 76.17; Н 5.78; N 10.25.
Synthesis of phthalocyanines (general procedure).
A substituted phthalocyanine, 0.5 mmol, was ground
with 63 mg (0.14 mmol) of magnesium acetate
tetrahydrate and 60 mg (1 mmol) of urea. The mixture
was heated at 180–195°С for 2 h. The reaction mass
was repreciptated from a glacial acetic acid solutions.
The precipitate was washed with distilled water. The
admixtures were extracted with ethanol–water, 1:1
(Ia–IVа) and acetone–water, 1:2 (Ib, IIb, Vb). The
targeted phthalocyanines were extracted with
chloroform. The final purification was performed by
column chromatography (adsorbent Al2O3, eluent
chloroform). The solvent was removed in a vacuum,
and the products were vacuum-dried at 80°С.
Tetra-4-(morpholin-4-yl)tetra-5-(2'-naphthyl-
oxy)phthalocyanine (IIIa) was obtained by the
general procedure from 80 mg of 4-(morpholin-4-yl)
tetra-5-(2'-naphthyloxy)phthalonitrile. Yield 66 mg
(37%). IR spectrum, ν, cm–1: 3299, 1007 (NH), 2868,
2836 (CH2), 1208 (Ar–O–Ar). Found, %: С 74.02; Н
5.08; N 11.97. С88H70N12O8. Calculated, %: С 74.25; Н
4.96; N 11.81.
Tetra-4-(morpholin-4-yl)tetra-5-(4'-chloro-3'-
methylphenoxy)phthalocyanine (IVa) was obtained
by the general procedure from 89 mg of 4-(morpholin-
4-yl)tetra-5-(4'-chloro-3'-methylphenoxy)phthalo-
nitrile. Yield 49 mg (55%). IR spectrum, ν, cm–1: 3297,
1007 (NH), 2871, 2835 (CH2), 1208 (Ar–O–Ar).
Found, %: С 64.21; Н 4.88; N 11.71. С76H66N12O8Cl4.
Calculated, %: С 64.41; Н 4.69; N 11.86.
The synthesized H2Рс(4-Het)4(5-R)4 are dark green
powders, they are readily soluble in water, con-
centrated HCl and H2SO4, glacial acetic acid, DMF,
chloroform, and some other organic solvents.
Tetra-4-(morpholin-4-yl)tetra-5-phenoxyphthalo-
cyanine (Ia) was obtained by the general procedure
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

SYNTHESIS AND PROPERTIES OF TETRA-4-MORPHOLINYL(PIPERIDINYL)-...
761
8. Tolbin, A.Yu., Sirotin, S.V., Moskovskaya, I.F.,
Tomilova, L.G., and Romanovskiy, B.V., Macro-
heterocycles, 2009, vol. 2, nos. 3–4, p. 261.
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Tetra-4-(piperidin-1-yl)tetra-5-phenoxyphthalo-
cyanine (Ib) was obtained by the general procedure
from 76 mg of 4-(piperidin-1-yl)tetra-5-phenoxy-
phthalonitrile. Yield 36 mg (47%). IR spectrum, ν, cm–1:
3324, 1007 (NH), 2870, 2834 (CH2), 1208 (Ar–O–Ar).
Found, %: С 76.29; Н 7.41; N 11.85. С76H70N12O4.
Calculated, %: С 75.10; Н 5.80; N 13.83.
Tetra-4-(piperidin-1-yl)tetra-5-{[3,4'-dimethyl-
(1,1'-biphenyl)-4-yl]oxy}phthalocyanine (IIb) was
obtained by the general procedure from 102 mg of 4-
(piperidin-1-yl)tetra-5-{[3,4'-dimethyl (1,1'-biphenyl)-
4-yl]oxy}phthalonitrile. Yield 56 mg (55%). IR
spectrum, ν, cm–1: 3320, 1006 (NH), 2866, 2832 (CH2),
1208 (Ar–O–Ar). Found, %: С 79.24; Н 6.52; N 10.01.
С108H102N12O4. Calculated, %: С 79.48; Н 6.30; N
10.30.
14. Shishkina, O.V., Maizlish, V.E., and Shaposhnikov G.P.,
Tetra-4-(piperidin-1-yl)tetra-5-(phenylsulfanyl)-
Zh. Obshch. Khim ., 2001, vol. 71, no. 2, p. 271.
phthalocyanine (Vb) was obtained by the general
procedure from 90 mg of 4-(piperidin-1-yl)tetra-5-
(phenylsulfanyl)phthalonitrile. Yield 35 mg (44%). IR
spectrum, ν, cm–1: 3324, 1008 (NH), 2930, 2830
(CH2), 1128 (Ar–S–Ar). Found, %: С 71.20; Н 5.87; N
13.01; S 9.52. С76H70N12S4. Calculated, %: С 71.33; Н
5.51; N 13.13; S 9.57.
15. Maizlish, V.E., Shirokov, A.V., Kudrik, E.V., and
Shaposhnikov, G.P., Zh. Obshch. Khim ., 2002, vol. 72,
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