Synthesis and properties of tetra- and octasubstituted metal pthalocyanines with alkylsulfamoyl groups

Article abstract of DOI:10.1023/B:RUGC.0000025521.67369.77

Sulfochlorination of sulfophenyl- and halosulfo-substituted copper and cobalt phthalocyanines and the subsequent reaction of the resulting sulfonyl chlorides with various alkylamines afforded a series of terra- and octasubstituted metal phthalocyanines containing alkylsulfamoyl groups. Their solubilities, spectral, and other physicochemical properties are dependent on the number and length of the alkyl radicals, the nature of the substituent combined with the alkylsulfamoyl group, and the nature of the complexing metal.

Full text of DOI:10.1023/B:RUGC.0000025521.67369.77

Russian Journal of General Chemistry, Vol. 74, No. 2, 2004, pp. 300 304. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 2, 2004,
pp. 334 337.
Original Russian Text Copyright
2004 by Lutsenko, Shaposhnikov, Kulinich.
Synthesis and Properties of Tetra- and Octasubstituted Metal
Pthalocyanines with Alkylsulfamoyl Groups
O. G. Lutsenko, G. P. Shaposhnikov, and V. P. Kulinich
Ivanovo State University of Chemical Technology, Ivanovo, Russia
Received March 1, 2002
Abstract Sulfochlorination of sulfophenyl- and halosulfo-substituted copper and cobalt phthalocyanines
and the subsequent reaction of the resulting sulfonyl chlorides with various alkylamines afforded a series of
tetra- and octasubstituted metal phthalocyanines containing alkylsulfamoyl groups. Their solubilities, spectral,
and other physicochemical properties are dependent on the number and length of the alkyl radicals, the nature
of the substituent combined with the alkylsulfamoyl group, and the nature of the complexing metal.
Over several decades metal complexes of substi-
tuted phthalocyanines have been drawing researcher’s
R2 R1
attention owing to their scientifically and practically
valuable properties [1, 2].
Among octasubstituted phthalocyanines, special
N
N
N
N
place belongs to compounds containing various sub-
stituents in their benzene rings. The problem of
synthesis and investigation of such compounds is of
urgent interest, since substituents of various nature
can impart to the obtained compounds solubility in
water, as well in polar and nonpolar organic solvents
[3].
N
N M
N
R1
R2
R2
R1
N
The present study deals with synthesis and pro-
perties of metal phthalocyanines containing alkylsul-
famoyl and other groups. As starting compounds for
the synthesis of complexes I XIII we used sulfo-
phenyl- and halosulfo-substituted copper and cobalt
phthalocyanines XIV XIX which were prepared by
the earlier developed procedure [4, 5].
R1 R2
I XXV
NHAlk2
or
NH2C18H37
SOCl2,
HSO3Cl
XIV XIX
XX XXV
I XIII,
M = Cu; R1 = C6H4SO2N(C8H17)2, R2 = H (I); R1 = Cl,
R2 = SO2N(C8H17)2 (V); R1 = Br, R2 = SO2N(C2H5)2 (IX);
Sulfonyl chlorides XX XXV were prepared by re-
actions of sulfo-substituted metal phthalocyanines
XIV XIX with thionyl chloride and chlorosulfonic
acid. Subsequent acylation of various alkylamines
(diethylamine, dioctylamine, octadecylamine) with
sulfonyl chlorides XX XXV gave compounds I XIII.
The reactions were carried out in organic solvents that
were chosen so that both the sulfonyl chloride and
amine were readily soluble.
R1 = Br, R2 = SO2N(C8H17)2 (X); M = Co; R1 = C6H4SO2
N(C2H5)2, R2 = H (II); R1 = C6H4SO2N(C8H17)2, R2 = H
(III); R1 = C6H4SO2NHC18H37, R2 = H (IV); R1 = Cl,
R2 = SO2N(C2H5)2 (VI); R1 = Cl, R2 = SO2N(C8H17)2
(VII); R1 = Cl, R2 = SO2NHC18H37 (VIII); R1 = Br, R2 =
SO2N(C2H5)2 (XI); R1 = Br, R2 = SO2N(C8H17)2 (XII);
R1 = Br, R2 = SO2NHC18H37 (XIII); M = Cu, R1
=
C6H4SO3H, R2 = H (XIV); M = Co, R1 = C6H4SO3H, R2 =
H (XV); M = Cu, R1 = Cl, R2 = SO3H (XVI); M = Co,
R1 = Cl, R2 = SO3H (XVII); M = Cu, R1 = Br, R2 = SO3H
(XVII); M = Co, R1 = Br, R2 = SO3H (XIX); M = Cu,
R1 = C6H4SO2Cl, R2 = H (XX); M = Co, R1 = C6H4SO2Cl,
R2 = H (XXI); M = Cu, R1 = Cl, R2 = SO2Cl (XXII); M =
Co, R1 = Cl, R2 = SO2Cl (XXIII); M = Cu, R1 = Br, R2 =
SO2Cl (XXIV); M = Co, R1 = Br, R2 = SO2Cl (XXV).
Compounds I XIII are powdery bluish green
water-insoluble substances. Their peculiar feature is
that they are readily soluble in polar and low-polarity
solvents (DMF, chloroform, carbon tetrachloride,
benzene, etc.). This property distinguishes them from
the starting sulfo-substituted metal phthalocyanines
1070-3632/04/7402-0300 2004 MAIK Nauka/Interperiodica

SYNTHESIS AND PROPERTIES OF TETRA- AND OCTASUBSTITUTED METAL
301
T, %
80
60
40
20
1
3000
1500
1000
500 , cm
Fig. 1. IR spectrum of CoPc(4-Cl) [5-SO N(C H ) ] .
4
2
8
17 2 4
D, rel. unis
D, rel. unis
(a)
(b)
1
0.75
0.50
0.25
0.75
0.50
0.25
2
1
2
500
600
700 800 , nm
500
600
700 800 , nm
Fig. 2. Electronic absorption spectra in (a) DMF {(1) CuPc(4-Cl) [5-SO N(C H ) ] and (2) CoPc(4-Br) [5-SO N(C H ) ] }
4
2
8
17 2 4
4
2
8 17 2 4
and (b) benzene {(1) CoPc(4-Cl) [5-SO N(C H ) ] and (2) CoPc(4-Br) [5-SO N(C H ) ] }.
4
2
8
17 2 4
4
2
8 17 2 4
and enables further studies to be performed in organic
media. It was also noted that compounds I, III, V,
VII, X, and XII are better soluble than other alkyl-
sulfamoyl-substituted metal phthalocyanines, probably
because of the specific structure of the dialkyl-
sulfamoyl radical.
C H bonds [7], as well as absorption bands at 1300
1400 cm , assignable to alkylsulfamoyl S=O bonds
[8].
1
The electronic absorption spectra (see table, Fig. 2)
in DMF show that introduction of various bulky alkyl-
sulfamoyl groups in the phthalocyanine molecule pro-
duces no significant changes in the spectral patterns.
The spectra all contain a strong Q band at 600
Compounds I XIII were identified on the basis of
their elemental analyses and UV and IR spectra. The
IR spectra at 500 3600 cm 1 (Fig. 1) are representative
of the phthalocyanine structure of the obtained com-
pounds. The spectra contain absorption bands at 804
700 nm, corresponding to
*-electron transition in
the phthalocyanine macroring. In going from DMF to
benzene (Fig. 2), the spectra acquire some atypical
features. As distinct from DMF solutions, the long-
wave Q band of benzene solutions has no well-defined
vibrational satellite (low-intensity band). Instead, an
1
900 and 1075 1290 cm , characteristic of all metal
phthalocyanines [6]. Furthermore, absorption bands
1
at 2800 3000 cm are observed, assignable to alkyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004

302
LUTSENKO et al.
Yields, Rf values, electronic absorption spectra, and elemental analyses of compounds I XIII
Electronic absorption
Found, %
Calculated, %
spectrum, max, nm
Rf
Formula
benzene
DMF H2SO4
C
H
N
S
C
H
N
S
I
II
44 0.74 687, 631 674, 610
23 0.88 687, 630 676, 608
68.3 7.1
59.7 5.3 11.2
70.0 7.1
69.2 8.5
60.3 7.1
8.5
6.9 C120H164CuN12O8S4
8.6 C72H68CoN12O8S4
5.5 C120H164CoN12O8S4
5.3 C128H180CoN12O8S4
68.8 7.8 8.0 6.1
61.0 4.8 11.9 9.0
68.9 7.8 8.0 6.1
69.8 8.2 7.6 5.8
III 39 0.90 685, 625 665, 606
IV 50 0.81 622, 671 675, 633
V
7.4
7.0
7.6
31 0.96 679, 628
786
6.1 C96H144Cl4CuN12O8S4 59.8 7.5 8.7 6.6
VI 38 0.74 670, 629
VII 40 0.97 676, 625
VIII 48 0.75 676, 610
IX 51 0.93 679, 637
46.6
786
3.2 12.9 11.0 C48H48Cl4CoN12O8S4 46.1 3.8 13.4 10.2
60.3 5.2
8.7
6.1 C96H114Cl4CoN12O8S4 59.9 5.9 8.4 6.7
6.8 C104H160Cl4CoN12O8S4 61.3 7.9 8.3 6.3
8.6 C48H48Br4CuN12O8S4 40.2 3.4 11.7 8.9
5.4 C96H144Br4CuN12O8S4 54.7 6.8 8.0 6.1
8.5 C48H48Br4CoN12O8S4 40.3 3.4 11.8 9.0
5.7 C96H144Br4CoN12O8S4 54.8 6.9 8.0 6.1
5.3 C104H160Br4CoN12O8S4 56.4 7.2 7.6 5.8
59.7 6.5
7.8
39.4 2.8 11.1
786, 752 55.1 6.1 8.7
39.9 2.9 11.3
X
34 0.86 679, 633
XI 51 0.88 670, 637
XII 38 0.91 676, 614
XIII 35 0.84 668, 625
786
54.4 6.6
56.1 6.8
7.3
7.3
ill-defined diffuse band or shoulder, depending on the
number and length of alkyl groups in the sulfamoyl
substituents, appears at the short-wave descend of the
Q band. The absorption intensity in this spectral
region in benzene is much higher than in DMF.
Similar spectral patters in low-polarity organic sol-
vents were earlier observed with other alkylsulfamoyl-
substituted phthalocyanines and can be explained by
molecular association [9, 10]. Thus, basing on pub-
lished data and judging from the spectral patterns of
the obtained compounds, we can admit that in
benzene solutions there exist both associated (
687 nm) and unassociated ( 630 nm) molecules,
dimers inclusive [11].
EXPERIMENTAL
The IR spectra were registered on a Specord M-80
1
instrument at 500 4000 cm . The electronic absorp-
tion spectra were taken in benzene, DMF, and H2SO4
on a Specord M-40 spectrophotometer at room tem-
perature at 400 800 nm.
Compounds I XIII. To 0.2 mmol of compound
XIV XIX, 4 ml of chlorosulfonic acid was added,
and then 5 ml of thionyl chloride was added with
stirring. The resulting mixture was held at 60 C for
4 h and then for 1 h at 75 80 C. After cooling, the
reaction mixture was poured onto ice with sodium
chloride. The precipitate that formed was filtered off
on a porous glass filter, washed with cooled saturated
aqueous solution of sodium chloride until a negative
Congo red test of washings. The reaction product was
dried in a vacuum and then brought in reaction with
alkylamines.
Analysis of the electronic absorption spectra of
certain of the obtained metal complexes in concen-
trated sulfuric acid (see table) revealed a general trend
in spectral changes in going from organic solvents to
sulfuric acid [12]. In this case, like with unsubstituted
and phenyl- or halogen-substituted metal phthalo-
cyanine complexes [13], a substantial (>100 nm)
bathochromic shift of the Q band was observed. This
observation is assignable to the protonation of the
phthalocyanine macroring by meso-nitrogen atoms.
The magnitude of this shift in our case is slightly
smaller than with unsubstituted and the correspond-
ing tetrasubstituted metal phthalocyanines, which can
be explained by the participation in protonation of
peripheral alkylsulfamoyl nitrogen atoms with con-
current decrease in the degree of protonation of meso-
nitrogen atoms.
Alkylamine (diethylamine, dioctylamine, or octa-
decylamine) was preliminarily dissolved in a little
(5 ml) organic solvent, and the obtained sulfonyl
chloride XX XXV was dissolved in the same organic
solvent. The reaction was carried out by refluxing the
reaction mixture for 4 5 h, filtered through a paper
filter, and the filtrate was evaporated. The final puri-
fication was made by column chromatography on
alumina or silica gel.
Copper tetra[4-(p-dioctylsulfamoyl)phenyl]-
phthalocyanine (I) was prepared from compound
XIV and dioctylamine in acetone. Column chromato-
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SYNTHESIS AND PROPERTIES OF TETRA- AND OCTASUBSTITUTED METAL
303
graphy was performed on Silica gel L 40/100, eluent
benzene etanol, 10:4.
Cobalt tetra(4-bromo-5-diethylsulfamoyl)-
phthalocyanine (XI) was prepared from compound
XIX and diethylamine in acetone. Column chroma-
tography was performed on alumina, eluent chloro-
form ethanol, 10:1.
Cobalt tetra[4-(p-diethylsulfamoyl)phenyl]-
phthalocyanine (II) was prepared from compound
XV and diethylamine in acetone. Column chromato-
graphy was performed on alumina, eluent acetone
chloroform, 10:1.
Cobalt tetra(4-bromo-5-dioctylsulfamoyl)-
phthalocyanine (XII) was prepared from compound
XIX and dioctylamine in acetone. Column chroma-
tography was performed on Silica gel L 40/100, eluent
benzene ethanol, 2:1.
Cobalt tetra[4-(p-dioctylsulfamoyl)phenyl]-
phthalocyanine (III) was prepared from compound
XV and dioctylamine in acetone. Column chromato-
graphy was performed on Silica gel L 40/100, eluent
benzene ethanol, 3:1.
Cobalt tetra(4-bromo-5-octadecylsulfamoyl)-
phthalocyanine (XIII) was prepared from compound
XIX and octadecylamine in acetone. Column chro-
matography was performed on alumina, eluent chlo-
roform ethanol, 10:1.
Cobalt tetra[4-(p-octadecylsulfamoyl)phenyl]-
phthalocyanine (IV) was prepared from compound
XV and octadecylamine in acetone. Column chroma-
tography was performed on Silica gel L 40/100, eluent
benzene ethanol, 10:4.
REFERENCES
1. Moser, F.H. and Thomas, A.L., The Phthalocyanine
Compounds, Boca Raton, 1983, vols. 1, 2.
Copper tetra(4-chloro-5-dioctylsulfamoyl)-
phthalocyanine (V) was prepared from compound
XVI and dioctylamine in acetone. Column chromato-
graphy was performed on Silica gel L 40/100, eluent
benzene ethanol, 5:1.
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phthalocyanine (X) was prepared from compound
XVIII and dioctylamine in acetone. Column chro-
matography was performed on Silica gel L 40/100,
eluent benzene ethanol, 2:1.
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22N292P.
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