Cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanines covalently supported on wool: Synthesis, characterization and catalytic activity

Article abstract of DOI:10.1142/S1088424616500589

Functionalized wool with cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanine (CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool) have been synthesized and their structures characterized by flame atomic absorption spectroscopy (FAAS), FT-IR, UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and the energy dispersive spectroscopy (EDS) analysis. The catalytic activity of the synthesized catalysts was investigated for the aerobic oxidation of alkyl arenes and alcohols to their corresponding carbonyl compounds in the absence of any co-promoter and additional oxidizing reagent. We found the best catalyst for the mentioned reactions is the CoTSPc@wool from the solvent, conversion, temperature, and reaction time point of views. The synthesized catalysts can be readily recycled and reused for several runs without significant loss of efficiency.

Full text of DOI:10.1142/S1088424616500589

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2016; 20: 1–12
DOI: 10.1142/S1088424616500589
Published at http://www.worldscinet.com/jpp/
Cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanines
covalently supported on wool: Synthesis, characterization
and catalytic activity
Ahmad Shaabani* and Zeinab Hezarkhani
Faculty of Chemistry, Shahid Beheshti University, G. C., P. O. Box 19396-4716 Tehran, Iran
Received 17 January 2016
Accepted 18 February 2016
ABSTRACT: Functionalized wool with cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanine
(
CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool) have been synthesized and their structures
characterized by flame atomic absorption spectroscopy (FAAS), FT­IR, UV­vis, X­ray diffraction (XRD),
thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and the energy dispersive
spectroscopy (EDS) analysis. The catalytic activity of the synthesized catalysts was investigated for the
aerobic oxidation of alkyl arenes and alcohols to their corresponding carbonyl compounds in the absence
of any co­promoter and additional oxidizing reagent. We found the best catalyst for the mentioned
reactions is the CoTSPc@wool from the solvent, conversion, temperature, and reaction time point of
views. The synthesized catalysts can be readily recycled and reused for several runs without significant
loss of efficiency.
KEYWORDS: wool, cobalt(II) tetrasulfophthalocyanine, copper(II) tetrasulfophthalocyanine, iron(II)
tetrasulfophthalocyanine, aerobic oxidation, green chemistry.
(ii) separation of the homogeneous MPc catalysts from
INTRODUCTION
the reaction media is difficult. To address these issues, it
has been shown that immobilization of the MPcs on the
insoluble and inert supports via covalent attachment not
only simplifies the separation process of the homogeneous
MPcs, but also increases the effective surface area of
the heterogeneous MPcs [2, 3]. Since the direction of
science and technology is shifting to emphasize more on
the environment­friendly reusable catalytic processes,
therefore, natural biopolymers are attractive candidates
to be used as solid supports for catalytic applications [4].
In addition, it is reported that the MPc catalysts, fixed on
the support, are more stable against radical species in the
oxidation reaction solution than the unfixed ones [1].
Metallophthalocyanines, as functional dyes, are used
widely in dyeing of textile, paper, leather, cellulose, wool,
etc. The soluble phthalocyanine dyes were obtained with
modification of the approximately insoluble phthalocy­
anines by introduction of various substituents. The salt
of phthalocyanine sulfonic acid is water­soluble and
sulfonated phthalocyanine was the first phthalocyanine
dye. The resulting water­soluble sulfonic acids can be
Phthalocyanines (Pcs) and metallophthalocyanines
MPcs) have been extensively investigated in applica­
(
tions such as electrophotography, catalysis, and infrared
radiation absorption, because of their excellent physical,
chemical, and coloristic properties [1]. By incorporating
of various kinds of catalytically active metals in the
phthalocyanine ligand, the related phthalocyanines
show variety of catalytic effects corresponding to the
metals used [1]. Representative examples are including
oxidation, dehydrogenation, gas­phase reactions, and
electrocatalysis.MPcshaveactivesitesofmetalloenzymes
that cause MPcs such as CoPc, CuPc, and FePc to be used
as efficient biomimetic homogeneous and heterogeneous
catalysts in catalytic oxidation processes [1]. However,
these durable catalysts have some limitations such as:
(
i) aggregation and agglomeration of the MPc complexes
that substantially affected their catalytic activity and
*
Correspondence to:Ahmad Shaabani, email: a­shaabani@sbu.
ac.ir, fax: +9821­22431661
Copyright © 2016 World Scientific Publishing Company

2
A. SHAABANI AND Z. HEZARKHANI
used in dyeing various substrates including textile, paper,
leather, cellulose, or wool [1, 5–7]. These sulfonated
phthalocyanines bear a reactive anchor group, which
help them to covalently bind to free amino­ or hydroxyl
groups of wool or cellulose. The dyeing procedure was
carried on in a two­stage process involving the adsorption
of dye to the substrate followed by fixing with reaction
of the anchor group with the fiber [1]. The wool fiber
is a very cheap natural biopolymer that composed of
protein filaments and consists mainly of keratin. The wool
biopolymer contains numerous amino acid units with
–
NH–CO–, –NH , and –S–S– functional groups and amino
2
acids in wool cross–linked by S–S bonds. These amino
groups of keratin in wool are of decisive importance for
the dyeing process.
Inviewofourinterestforthesynthesisofmetallophtha­
locyanines and their applications in oxidation of organic
compounds [3, 8–11], herein, we report the synthesis of
CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool and
investigate their catalytic activity in the aerobic oxidation
of various of benzylic hydrocarbons and alcohols. It is
important to note that the aerobic oxidation of benzylic
hydrocarbons and alcohols using MTSPc@wool did not
proceed without air blowing.
RESULTS AND DISCUSSION
The synthesized catalysts were characterized by
FAAS, FT­IR, UV­vis, XRD, TGA, SEM, and EDS
analysis. The Co(II), Cu(II), and Fe(II) content of the
MTSPc@wool catalysts was determined using FAAS
method. The amounts of CoTSPc, CuTSPc, and FeTSPc
in the CoTSPc@wool, CuTSPc@wool, FeTSPc@wool
catalysts were determined 0.42%, 0.71%, and 0.80%,
respectively. Covalent immobilization of the cobalt(II),
copper(II), and iron(II) as tetrasulfophthalocyanines on
wool fibers was confirmed by FT­IR spectroscopy. The IR
spectrums of the synthesized CoTSPc@wool, CuTSPc@
wool, and FeTSPc@wool catalysts show absorption
Fig. 1. FT­IR spectra of wool, CoTSPc@wool, CuTSPc@wool,
and FeTSPc@wool
−
1
bands at 1655, 1639, and 1635 cm , respectively, indicate
a characteristic band for C=N bonds of phthalocyanines
(
Fig. 1).
Also, the amounts of CoTSPc, CuTSPc, and FeTSPc in
the CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool
catalysts were measured using UV­vis method (Fig. 2) as
follows. The catalyst was dissolved in H SO (3.0 mL) with
2
4
sonication and the mixture was filtered. The total volume
of the filtrate made up to about 50 mL with H O. The
2
cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanine
concentration was obtained using calibration curves
prepared with CoTSPc, CuTSPc, and FeTSPc solution
standards, respectively. The obtained result was consistent
with result of FAAS method.
Fig. 2. UV­vis spectrums of wool and the synthetic catalysts in
H O:H SO (17:1)
2 2 4
The XRD patterns of wool, MTSPc, and MTSPc@
wool were employed to investigate the structure of the
synthetic catalysts. As shown the XRD pattern of wool
fibers in Fig. 3, the characteristic diffraction peaks
of wool fibers appear as two broad peaks at 2q values
of around 9° and 21° (Fig. 3­I). The XRD patterns of
CoTSPc@wool (III), CuTSPc@wool (V), and FeTSPc@
wool (VII) are shown in Fig. 3, as well. In all of them, the
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 2–12

COBALT(II), COPPER(II), AND IRON(II) TETRASULFOPHTHALOCYANINES COVALENTLY SUPPORTED ON WOOL
3
Fig. 3. XRD patterns of wool (I), CoTSPc (II), CoTSPc@wool (III), CuTSPc (IV), CuTSPc@wool (V), FeTSPc@wool (VI) and
FeTSPc@wool (VII)
Fig. 4. TG curves of wool (I) and covalently supported MTSPc on wool fibers (CoTSPc@wool (II), CuTSPc@wool (III), and
FeTSPc@wool (IV) in air
very weak characters of CoTSPc, CuTSPc, and FeTSPc
were observable. This means that the CoTSPc, CuTSPc,
and FeTSPc dispersed completely onto the surface of
wool fibers as molecular dispersion.
The thermal stability of MTSPc@wool catalysts
was verified by thermogravimetric analysis. Thermo­
gravimetric curves for natural wool and the prepared
catalysts are shown in Fig. 4. The results related to
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 3–12

4
A. SHAABANI AND Z. HEZARKHANI
Fig. 5. SEM images of wool (a) and covalently supported MTSPc on wool fibers (CoTSPc@wool (b), CuTSPc@wool (c), FeTSPc@
wool (d))
TGA curves of wool, CoTSPc@wool, CuTSPc@
wool, and FeTSPc@wool revealed after initial loss of
adsorbed water at 90–239°C, 86–242°C, 81–235°C,
and 83–238°C, respectively, the main loss of weight
occurred. The decomposition step seems to include two
stages up to 800°C and this loss was attributed to the first
step of decomposition reaction at about 239°C, 242°C,
of indane in presence of CoTSPc@wool and CuTSPc@
wool catalysts (Table 1, Entries 5, 15). In the case of
FeTSPc@wool catalyst, CH CN/H O (2/1) was used as
3
2
the preferred solvent (Table 1, Entry 25). The comparison
of the results related to affect of various amounts of
CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool
catalysts revealed that the 0.5 mol% of CoTSPc, 2.6 mol%
of CuTSPc, and 3.0 mol% of FeTSPc provide the best
results. Also, the CoTSPc@wool, CuTSPc@wool, and
FeTSPc@wool catalysts have better catalytic role than
aggregated CoTSPc, CuTSPc and FeTSPc, respectively
(Entries 1, 5, 11, 15 and 21, 25) and one of the reasons
for the higher activity of phthalocyanine supported on the
wool fibers may be seen in the increasing concentration
of monomeric catalyst molecules [1]. The best result
for the oxidation of indane was found at the reaction
temperature of 100°C, 100°C, and 80°C for CoTSPc@
wool, CuTSPc@wool, and FeTSPc@wool catalysts,
respectively.
2
3
35°C, and 238°C and the second one at 380°C, 371°C,
69°C, and 395°C, respectively.
The SEM analyses have been used to study the struc­
ture and morphology of the obtained CoTSPc@wool,
CuTSPc@wool, and FeTSPc@wool catalysts (Fig. 5).
Since cobalt(II), copper(II) and iron(II) tetrasulfophth­
alocyanines covalently supported on the wool, the aggre­
gation should not occur on the wool fiber surface. The
SEM images of CoTSPc@wool, CuTSPc@wool, and
FeTSPc@wool catalysts did not show any aggregation
and confirmed that MTSPc covalently supported and
well­dispersed on the surface of wool fibers.
Additionally, the energy dispersive spectroscopy
Finally, the oxidation of the various alkyl arenes to
(
EDS)analysis, thatdeterminedthechemicalcomposition
related carbonyl compounds was carried out in H O as
2
of CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool,
proves the presence of cobalt, copper, and iron in the
catalysts (Fig. 6) [16–18].
the preferred solvent for COTSPc@wool catalyst (1.0 g,
0.5 mol%) and CuTSPc@wool (3.2 g, 2.6 mol%) and
CH CN/H O (2/1) for FeTSPc@wool (3.3 g, 3.0 mol%)
3
2
Aerobic oxidation of indane was selected as a model
reaction to achieve a suitable catalytic system for the
aerobic oxidation using MTSPc@wool catalysts in the
(Table 2).
As indicated in Table 2, water has been used as a
environment friendly solvent in the oxidations of the alkyl
arenes using CoTSPc@wool and CuTSPc@wool. Thus,
the oxidation using the CoTSPc@wool and CuTSPc@
reaction media. As indicated in Table 1, H O as the
2
preferred solvent was selected for the aerobic oxidation
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 4–12

COBALT(II), COPPER(II), AND IRON(II) TETRASULFOPHTHALOCYANINES COVALENTLY SUPPORTED ON WOOL
5
Fig. 6. EDS result for CoTSPc@wool (I), CuTSPc@wool (II), FeTSPc@wool (III)
wool catalysts have the advantage to be carried out in
more green reaction conditions, but the reaction in the
precence of CoTSPc@wool has been carried out in lower
amount of catalyst. CoTSPc@wool and CuTSPc@wool
catalysts were placed in the first and second position
considering the mentioned criteria, respectively. Between
these three catalytic systems, the FeTSPc@wool has
the third place. To carry out oxidation reaction using
FeTSPc@wool catalyst, the mixed solvent acetonitrile/
The usability of these CoTSPc@wool, CuTSPc@
wool, and FeTSPc@wool catalytic systems have been
examined for the aerobic oxidation of the alcohols as well.
The aerobic oxidation of 1­indanol, as a model substrate,
by these catalysts was optimized (Table 3). The efficiency
of CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool
catalysts in H O, H O, and acetonitrile/H O as solvent
was higher than other solvents, respectively. The best
result in Table 3, Entries 5, 12, and 19, are related to the
CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool
2
2
2
H O was used at 80°C.
2
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J. Porphyrins Phthalocyanines 2016; 20: 5–12

6
A. SHAABANI AND Z. HEZARKHANI
Table 1. Optimization of the reaction conditions for the aerobic oxidation of alkyl arenes by CoTSPc, CuTSPc, FeTSPc, CoTSPc@
a,b,c
wool, CuTSPc@wool, and FeTSPc@wool catalysts
d
Entry
Catalyst
Amount of catalyst
metal mol%)
Solvent
Time, h
Temperature, °C
Conversion, %
(
­
3
1
2
3
4
5
6
7
8
9
CoTSPc
5.0 × 10 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
0.8 g (0.4)
0.6 g (0.3)
1.0 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
H O
10
14
14
14
10
10
10
10
10
10
12
14
14
14
12
12
12
12
12
12
15
18
18
18
15
15
15
15
15
15
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
90
54
79
72
56
93
68
50
81
69
53
39
81
69
51
90
69
42
77
59
50
38
76
72
64
91
74
61
79
60
2
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CuTSPc
DMF
THF
CH CN
3
H O
2
H O
2
H O
2
H O
2
H O
2
80
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
H O
2
70
­
2
2.0 × 10 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
2.5 g (2.0)
1.8 g (1.4)
3.2 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
H O
2
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
90
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
FeTSPc
DMF
THF
CH CN
3
H O
2
H O
2
H O
2
H O
2
H O
2
80
H O
70
2
­
2
3.0 × 10 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
2.7 g (2.5)
2.2 g (2.0)
3.3 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
CH CN/H O (2/1)
Ref.
Ref.
Ref.
Ref.
80
3
2
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
H O
2
CH CN
3
DMF
CH CN/H O (2/1)
3
2
CH CN/H O (2/1)
80
3
2
CH CN/H O (2/1)
80
3
2
CH CN/H O (2/1)
70
3
2
CH CN/H O (2/1)
60
3
2
3
CH CN/H O (2/1)
50
46
3
2
a
b
Reaction conditions for CoTSPc and CoTSPc@wool catalysts: indane (1.0 mmol), solvent (10 mL), air as oxidant. Reaction
c
conditions for CuTSPc and CuTSPc@wool catalysts: indane (1.0 mmol), solvent (10 mL), air as oxidant. Reaction conditions for
FeTSPc and FeTSPc@wool catalysts: indane (1.0 mmol), solvent (10 mL), air as oxidant. Conversion determined by GC analysis.
d
catalyst, respectively. Similar to the oxidation of alkyl
arenes, using support for MTSPc increase the conversion
of the oxidation of alcohols (Table 3, Entries 1, 5, 8, 12
and 15, 19). In the case of oxidation of the alcohols, the
order of the catalysts can be regarded as CoTSPc@wool
been studied and the results obtained are presented in
Table 4. The mentioned reactions were done under air
blowing at room temperature for CoTSPc@wool and
CuTSPc@wool and 50°C for FeTSPc@wool catalyst
with good to high conversions. Selectivity for the aerobic
oxidation of alcohols to the related carbonyl compounds
using MTSPc@wool catalysts was observed and these
oxidation reactions were proceeded selectively and
effectively without any overoxidation to carboxylic acid
during the reaction.
>
CuTSPc@wool > FeTSPc@wool, based on using the
green solvent and milder reaction conditions.
To extend the scope of the CoTSPc@wool, CuTSPc@
wool, and FeTSPc@wool catalysts, the oxidation of
the alcohols to the related carbonyl compounds have
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COBALT(II), COPPER(II), AND IRON(II) TETRASULFOPHTHALOCYANINES COVALENTLY SUPPORTED ON WOOL
7
a,b,c
Table 2. Aerobic oxidation of various alkyl arenes to corresponding ketones
d
d
Entry
1
Alkyl arene
Product
Catalyst
Time, h Conversion, % Selectivity, %
O
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
13
16
17
13
16
17
14
18
18
10
13
15
10
12
15
10
12
12
14
18
18
15
17
18
12
14
14
94
83
87
90
86
85
82
78
79
93
84
89
93
90
91
97
92
89
91
86
83
87
80
84
92
88
89
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
>ꢀ99
> ꢀ9 9
> ꢀ9 9
> ꢀ9 9
> ꢀ9 9
> ꢀ9 9
> ꢀ9 9
O
2
3
4
5
6
7
8
O
O
O
O
O
O
O
O
O
O
O
9
a
Reaction conditions for CoTSPc@wool catalyst: alkyl arene (1.0 mmol), CoTSPc@wool (1.0 g), H O (10 mL), air as oxidant,
2
b
reflux. Reaction conditions for CuTSPc@wool catalyst: alkyl arene (1.0 mmol), CuTSPc@wool (3.2 g), H O (10 mL), air as
oxidant, reflux. Reaction conditions for FeTSPc@wool catalyst: alkyl arene (1.0 mmol), FeTSPc@wool (3.3 g), CH CN/H O
(
2
c
3
2
d
10 mL), air as oxidant, 80°C. Conversion and selectivity determined by GC analysis.
To select the best catalyst, the oxidation of 1­indanol
of Table 5 it can be clarified that the best catalyst is
CoTSPc@wool.
Recyclability of the CoTSPc@wool, CuTSPc@wool,
andFeTSPc@woolwasexaminedintheaerobicoxidation
of indane and 1­indanol. For this reason, MTSPc@wool
was studied in the same reaction conditions including
same solvent, temperature, and time (Table 5). The
oxidation of 1­indanol was done in water, as the
green solvent, and room temperature. From the data
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J. Porphyrins Phthalocyanines 2016; 20: 7–12

8
A. SHAABANI AND Z. HEZARKHANI
Table 3. Optimization of the reaction conditions for the aerobic oxidation of alcohols by CoTSPc, CuTSPc, FeTSPc, CoTSPc@
a,b,c
wool, CuTSPc@wool, and FeTSPc@wool catalysts
d
Entry
Catalyst
Amount of catalyst
metal mol%)
Solvent
Time, h
Temperature, °C Conversion, %
(
­
3
1
2
3
4
5
6
7
8
9
CoTSPc
5.0 × 10 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
1.0 g (0.5)
0.8 g (0.4)
0.6 g (0.3)
H O
8
12
12
12
8
rt
rt
53
86
74
60
92
78
61
47
71
59
46
89
68
59
43
80
75
72
91
80
66
77
61
2
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CoTSPc@wool
CuTSPc
DMF
THF
rt
CH CN
rt
3
H O
2
rt
rt
H O
2
8
H O
8
rt
2
­
2
2.0 × 10 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
3.2 g (2.6)
2.5 g (2.0)
1.8 g (1.4)
H O
2
10
12
12
12
10
10
10
10
12
12
12
10
10
10
10
10
rt
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
CuTSPc@wool
FeTSPc
DMF
THF
rt
1
1
1
1
1
1
1
1
1
1
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
rt
CH CN
rt
3
H O
2
rt
rt
H O
2
H O
2
rt
­
2
3.0 × 10 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
3.3 g (3.0)
2.7 g (2.5)
2.2 g (2.0)
3.3 g (3.0)
3.3 g (3.0)
CH CN/H O (2/1)
50
50
50
50
50
50
50
40
30
3
2
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
FeTSPc@wool
H O
2
CH CN
3
DMF
CH CN/H O (2/1)
3
2
CH CN/H O (2/1)
3
2
CH CN/H O (2/1)
3
2
CH CN/H O (2/1)
3
2
2
CH CN/H O (2/1)
3 2
a
b
Reaction conditions for CoTSPc and CoTSPc@wool catalysts: 1­indanol (1.0 mmol), solvent (10 mL), air as oxidant. Reaction
c
conditions for CuTSPc and CuTSPc@wool catalysts: 1­indanol (1.0 mmol), solvent (10 mL), air as oxidant. Reaction
conditions for FeTSPc and FeTSPc@wool catalysts: 1­indanol (1.0 mmol), solvent (10 mL), air as oxidant. Conversion
d
determined by GC analysis.
catalyst which was recovered from reaction media by
filtration was reused for four repetitive cycles in the
reaction after drying under vacuum at 70°C. As indicated
in Fig. 7 only minor decreases in the reaction conversions
were observed and the activity of the catalyst was saved
during successive uses.
As indicated in Table 6, the results of our investigations
are compared with previous reports of oxidation by
MPc [10, 11, 16–21].
obtained from Aldrich or Merck and used without further
purification. Co(II), Cu(II), and Fe(II) determination
was carried out on an FAAS (Shimadzu model AA­680
flame atomic absorption spectrometer) with a Co, Cu,
and Fe hollow cathode lamps at 240.7 nm, 324.7 nm,
and 248.3 nm, respectively, using an air­acetylene flame.
FT­IR spectra were recorded on a Shimadzu IR­470
spectrometer. UV­vis spectra were recorded employing an
Analytik Jena Specord S600 Diode Array spectrometer.
X­ray diffraction (XRD) pattern of catalysts was recorded
on a STOE STADI P with scintillation detector, secondary
monochromator using Cu Ka radiation (l = 0.1540 nm).
Thermogravimetric analysis (TGA) was carried out using
EXPERIMENTAL
­1
STA 1500 instrument at a heating rate of 10°C min in
air. Scanning electron microscopy (SEM) observations
were carried out on an electron microscopy Philips XL­30
ESEM. All samples were sputtered with gold before
observation. Microwave irradiation experiment was carried
General
Natural white wool (sheep of Kangavar/Iran) was
washed with NaOH solution, distilled water, methanol,
and acetone, and then cut into pieces. All reagents were
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 8–12

COBALT(II), COPPER(II), AND IRON(II) TETRASULFOPHTHALOCYANINES COVALENTLY SUPPORTED ON WOOL
9
a,b,c
Table 4. Selective aerobic oxidation of various alcohols to the corresponding aldehydes and ketones
d
d
Entry
1
Alcohol
OH
Product
Catalyst
Time, h Conversion, % Selectivity, %
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
9
12
12
9
91
88
87
91
90
85
88
84
83
93
90
91
91
87
89
92
89
90
92
89
91
96
92
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
CHO
CHO
OH
2
3
4
5
6
7
12
12
9
MeO
F
MeO
F
CHO
OH
12
12
9
CHO
OH
12
12
9
Cl
Cl
CHO
OH
12
12
9
O N
2
O N
2
OH
O
12
12
8
OH
O
10
10
7
OH
O
8
9
10
FeTSPc@wool
10
85
>99
OH
O
CoTSPc@wool
CuTSPc@wool
6
8
94
90
>99
>99
FeTSPc@wool
CoTSPc@wool
CuTSPc@wool
8
9
93
82
81
>99
>99
>99
OH
O
12
1
0
FeTSPc@wool
12
79
>99
a
Reaction conditions for CoTSPc@wool catalyst: alcohol (1.0 mmol), CoTSPc@wool (1.0 g), H O (10 mL), air as oxidant, rt.
2
b
c
Reaction conditions for CuTSPc@wool catalyst: alcohol (1.0 mmol), CuTSPc@wool (3.2 g), H O (10 mL), air as oxidant, rt.
2
Reaction conditions for FeTSPc@wool catalyst: alcohol (1.0 mmol), FeTSPc@wool (3.3 g), CH CN/H O (10 mL), air as oxidant,
3
2
d
5
0°C. Conversion and selectivity determined by GC analysis.
out in a Microsynth Milestone SRL microwave apparatus.
Products were analyzed using a Varian 3900 GC.
Synthesis of MTSPc. The metal(II) phthalocyanines
(MPcs) were synthesized by controlled microwave heating
of homogeneous powder, containing phthalic anhydride
(
0.88 g, 6.0 mmol), urea (1.6 g, 26 mmol), metal(II)
sulfate (1.8 mmol) and ammonium heptamolybdate
0.02 g, 0.02 mmol) according to our previously reported
Synthesis of metal(II) tetrasulfophthalocyanine
(
MTSPc) and metal(II) tetrasulfophthalocyanine
(
supported on wool (MTSPc@wool)
procedures [3, 8, 9]. The metal(II) tetrasulfophthalocy­
anines (MTSPc) were prepared directly from the sulfona­
tion of the synthesized MPcs according to published
Metal(II) tetrasulfophthalocyanine supported on wool
is prepared as Scheme 1.
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 9–12

10
A. SHAABANI AND Z. HEZARKHANI
Table 5. Comparison of the efficiency of the MTSPc@wool catalysts in same
solvent (H O), time (6 h), and temperature (room temperature) for the oxidation
2
a
of 1­indanol
OH
O
Catalyst
CoTSPc@wool
83
CuTSPc@wool
61
FeTSPc@wool
21
b
Conversion
a
Reaction conditions: 1­indanol (1.0 mmol), catalyst (1.0 g of CoTSPc@wool, 3.2 g
of CuTSPc@wool, and 3.3 g of FeTSPc@wool), H O (10 mL), air as oxidant, rt, 6 h.
2
b
Conversion determined by GC analysis.
Table 6. Comparison of the results obtained from MPc and supported MPc for the oxidation of 1–phenylethanol (M = Co) and
benzylalcohol (M = Cu and Fe)
Entry
Catalyst
Conditions
Molar ratio
substrate to catalyst, s
MPc
TOF of
Conversion, %
Ref.
­1
­
­
­
­
­
­
­
­
­
­
­
­
­
­
­
3
2
2
3
5
2
2
3
3
4
2
3
3
3
4
1
2
3
4
5
6
7
8
9
CoPc
CoPc
[bmim]Br/O /70°C /170 min
1:0.050
1:0.050
1:0.003
1:0.005
1:0.800
1:0.005
1:0.004
1:0.010
1:0.007
1:0.026
1:0.004
1:0.130
1:0.035
1:0.024
1:0.030
1.6 × 10
1.7 × 10
3.1 × 10
5.7 × 10
3.1 × 10
2.8 × 10
2.3 × 10
8.8 × 10
6.8 × 10
7.8 × 10
2.2 × 10
1.4 × 10
1.5 × 10
2.3 × 10
6.7 × 10
80
95
100
92
36
25
98
95
94
88
97
100
94
99
87
[19]
[20]
2
Xylene/O /KOH/ref./3 h
2
CoPcCl–APTES@SiO2 Solvent free/H O /ref./3 h
[21]
2
2
CoTSPc@wool
CuPc–MCM–41
CuPc
H O/air/rt/9 h
2
This work
[22]
Dioxane/TBHP/100°C/4 h
H O/TBAOX/70°C/0.5 h
2
[23]
CuTSPc@3D–(N)GFs
CuTAPc@cellulose
CuTSPc@cellulose
CuTSPc@wool
GO–FePc
H O/air/rt/3 h
2
[10]
toluene/air/40°C/3 h
[3]
H O/air/rt/5.5 h
2
[3]
1
1
1
1
1
1
0
1
2
3
4
5
H O/air/rt/12 h
2
This work
[11]
H O/O /60°C/3 h
2
2
FePc
CH Cl /IBX/rt/1.5 h
[24]
2
2
FeTAPc@cellulose
FeTSPc@cellulose
FeTSPc@wool
CH CN/air/40°C/5 h
[3]
3
CH CN/H O/air/40°C/5 h
[3]
3
2
CH CN/H O/air/50°C/12 h
This work
3
2
Fig. 7. Successive use of the prepared MTSPc@wool catalysts for the oxidation of indane and 1–indanol
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 10–12

COBALT(II), COPPER(II), AND IRON(II) TETRASULFOPHTHALOCYANINES COVALENTLY SUPPORTED ON WOOL
11
Scheme 1. Preparation of MTSPc@wool
reports [12, 13]. After successful preparation of MTSPc,
the synthesis of trisulfophthalocyanine sulfonyl chloride
was done by chlorosulfonation of sulfophthalocyanine
using an excess of chlorosulfuric acid [3, 6, 14].
Synthesis of MTSPc@wool. The synthesis of
MTSPc@wool was done, inspired by previously reported
procedure for dyeing of nitrogenous fibrous material,
i.e. dyeing of fibers including nitrogen in their chemical
constitution [15].
the absence of additional oxidizing reagent, excellent
conversion, very easy workup, the recyclability of
catalyst with no loss in its activity are other advantages
of these MTSPc@wool catalysts. All of the MTSPc@
wool catalysts have a high ability to selective and
effective aerobic oxidation of alkyl arenes and alcohols,
but the CoTSPc@wool is the best one from the solvent,
conversion, temperature, and reaction time viewpoints.
The order of the usability of the MTSPc@wool catalysts
for the aerobic oxidation of the alkyl arenes and alcohols
is CoTSPc@wool > CuTSPc@wool > FeTSPc@wool,
considering the lower thermal requirement of the
reactions and using green solvent in the reaction.
Oxidation of alkyl arenes and alcohols; general
procedure. In a typical reaction, an alkyl arene or
alcohol (1.0 mmol), MTSPc@wool, and solvent (10 mL
water for CoTSPc@wool and CuTSPc@wool and
CH CN/H O (2/1) for FeTSPc@wool) were added to
3
2
a two­necked flask. The mixture was stirred under air
blowing at the indicated temperature in the Tables 2 and 4.
Acknowledgements
We gratefully acknowledge financial support from the
Iran National Elites Foundation (INEF) and the Research
Council of Shahid Beheshti University.
­
1
Air was bubbled at a rate of 5 mL.min . The thin layer
chromatography (TLC) and gas chromatography (GC)
methods were used to investigate the progress of the
reaction. After completion of reaction and then filtration,
the crude product was extracted from reaction media
using EtOAc. The extracted solution analyzed by GC
method.
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