(E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II)and Cu(II)phthalocyanines and their catalytic activities on the oxidation of phenols

Article abstract of DOI:10.1016/j.jorganchem.2019.05.012

Phenols from various man-made activities pose threats to public health and aquatic ecosystems. A number of technologies (e.g., adsorption, oxidation, and biological methods)have been proposed and tested to remove phenolic compounds from different sources. Among these technologies, oxidation process is considered one of the most efficient tools for abating phenolic compounds because of low cost, easy scalability, and ecofriendly production. In this work, we aim to synthesize and characterize potential catalysts (Co(II)and Cu(II)phthalocyanines 6 and 7)for phenolic compounds oxidation. Different parameters influenced the oxidation process were determined and phenolic compounds oxidize to the less harmful products with high conversion and yield in the presence of Co(II)and Cu(II)phthalocyanine catalysts.

Full text of DOI:10.1016/j.jorganchem.2019.05.012

Accepted Manuscript
(E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II) and
Cu(II) phthalocyanines and their catalytic activities on the oxidation of phenols
Ece Tuğba Saka, Nuran Kahriman
PII:
S0022-328X(19)30193-7
DOI:
https://doi.org/10.1016/j.jorganchem.2019.05.012
JOM 20794
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 6 February 2019
Revised Date: 9 May 2019
Accepted Date: 13 May 2019
Please cite this article as: Ece.Tuğ. Saka, N. Kahriman, (E)-4-(4-(3-(2-fluoro-5-
(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II) and Cu(II) phthalocyanines and their
catalytic activities on the oxidation of phenols, Journal of Organometallic Chemistry (2019), doi: https://
doi.org/10.1016/j.jorganchem.2019.05.012.
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ACCEPTED MANUSCRIPT
(E)-4-(4-(3-(2-fluoro-5-
(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II)
and Cu(II) Phthalocyanines and Their Catalytic Activities on
The Oxidation of Phenols
*a
a
Ece Tuğba Saka , Nuran Kahriman
a
Department of Chemistry, Faculty of Science, Karadeniz Technical University, 61080
Trabzon, Turkey
Abstract
Phenols from various man-made activities pose threats to public health and aquatic
ecosystems. A number of technologies (e.g., adsorption, oxidation, and biological
methods) have been proposed and tested to remove phenolic compounds from different
sources. Among these technologies, oxidation process is considered one of the most
efficient tools for abating phenolic compounds because of low cost, easy scalability, and
ecofriendly production. In this work, we aim to synthesize and characterize potential
catalysts (Co(II) and Cu(II) phthalocyanines 6 and 7) for phenolic compounds oxidation.
Different parameters influenced the oxidation process were determined and phenolic
compounds oxidize to the less harmfull products with high conversion and yield in the
presence of Co(II) and Cu(II) phthalocyanine catalysts.
Keywords: Phenols; Phthalocyanine; Cobalt; Copper; Oxidation
Corresponding author. Tel.: +90 462 377 3666; fax: +90 462 325 3196.
E-mail address: ece_t_saka@hotmail.com (E.T. Saka).
1

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1
. Introduction
Phenolic compounds are widely used in different industries including paints,
fertilizers, surfactants, explosives, textiles, rubbers, plastics, curing agents, and
antioxidants [1]. The exposure to phenols and its derivatives poses a serious problem to the
human being as well as to the environment, due to which they are tagged as hazardous and
top priority pollutants. Phenolic wastewater has carcinogenic, teratogenic and mutagenic
influences on the growth and reproduction of aquatic organisms and contaminates drinking
water sources [2-3]. Phenolic compounds are classified by the US Environmental
Protection Agency as priority pollutants and negatively affect the taste and odor of water in
concentrations as low as 0.5 mg/ L. Additionally, they can be easily absorbed through skin
contact, potentially acting as potent endocrine disruptors [4-5].
Metal phthalocyanines (MPcs) are very useful and versatile class of organic
chromophores. Both usubstituted and substituted phthalocyanines of transition metals are
widely used as active layers of chemical sensors [6-8]. Introduction of electron donating or
withdrawing substituents to phthalocyanine macrocycles has been shown to change the
activity of MPcs to various substrates due to modification of both the electronic
distribution in the aromatic macrocycle and the molecule energetic levels [9–12]. Electron
withdrawing fluorine substituents decrease the electron density of the aromatic macrocycle
and increase the oxidation potential of the MPc molecule [9–12]. This makes the
fluorosubstituted phthalocyanines more active to the reducing different pheonls [13].
Cobalt phthalocyanine (CoPc), which is constituted by a cobalt atom located in the central
cavity of a two-dimensional structure consisting of 18-π electron aromatic macrocycle, has
attracted great interests as a catalyst because of its remarkable chemical properties and
2

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thermal stability [14-16]. Because of these reasons, we choosed fluorine groups to
synthesize Co(II) and Cu(II) phthalocyanines.
Some previously reported catalysts are summarized in Table 1. Different
peripherally groups substituted cobalt(II), iron(II), manganese(III), copper(II)
phthalocyanines were investigated on 2,6-di-tert-buthylphenol, 2,4,6-trichlorophenol,
2
3
,4,5-trichlorophenol, 2,3,6-trimethylphenol and p-nitrophenol oxidation [17-24]. In Table
, tetrasulfonated iron phthalocyanine was used in trichlorophenol oxidation reaction with
H O oxygen source. In the same work, 24% reaction conversion was obtained 24 h at 25
2
2
o
C. According to Table 3, two oxidation works with H O oxygen source were carried out
2
2
tetrasulfonated cobalt phthalocyanine and octacationic iron phthalocyanine catalyst. The
o
former employees 2,4,5 trichlorophenol oxidation reaction 24 h at 75 C with 67%
o
conversion and the latter was used trichlorophenol oxidation reaction 10 min. at 25 C with
6
% conversion. By comparing the catalyst in these literatures, it is inferred that the
compound 6 will be interesting catalyst in 2,3-dichlorophenol oxidation. In our previous
work, tetrasubstituted Co(II) and Fe(II) phthalocyanine complexes were studied as catalyst
in the oxidation of phenolic compounds [25-31]. In this work, firstly (2E)-3-[2-fluoro-5-
(
trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one 3, (E)-4-(4-(3-(2-fluoro-5-
trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile 5 and then cobalt(II) 6 and
(
copper(II) 7 phthalocyanines have been synthesized and characterized with spectral data
1
13
(
IR, H-NMR, C-NMR, UV-Vis, mass spectroscopies). Secondly, oxidation of different
phenolic compounds (4-nitrophenol, 3-chlorophenol, 2,3-dichlorophenol, 3-
methoxyphenol) was chosen as the model reaction to study the catalytic activity of the
synthesized Co(II) and Cu(II) phthalocyanines.
3

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2
. Experimental
The used materials, equipments and the general procedure for the oxidation of
phenolic compounds were reported as supplementary information.
2
2
.1. Synthesis
.1.1.(2E)-3-[2-fluoro-5-(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one (3)
Chalcone compound 3 was synthesized via Claisen-Schmidt condensation using NaOH as
a catalyst. 4'-hydroxyacetophenone (1.36 g, 10 mmol) and NaOH (0.80 g, 20 mmol) were
dissolved in a mixed solvent of H O (100 mL) /ethanol (50 mL) in a flask and stirred for
2
half an hour. Then, the ethanol solution of 2-fluoro-5-(trifluoromethyl)benzaldehyde (1.92
g, 10 mmol) was added drop by drop and reaction mixture was stirred for 24 h in room
temperature. The reaction was followed and monitored by TLC. After the reaction was
completed, 0.1 N HCl was added until the pH value was about 6. The solid product was
filtered and washed with cold chloroform and then water. The obtained compound was
dried with a freezedryer and the purity was checked with TLC. The yield 2.23 g (72%).
−
1
M.p.: 144–146 °C. Rf : 0.70 (Ether). FT-IR (cm ): 3356 (O-H), 3058 (Ar-H), 1655 (C=O),
1
1
569 (HC=CH), 1109 (Arom. C-F), 835 (Aliph. C-F). H NMR (400 MHz, DMSO-d ,
6
ppm): δ=7.8 (AB, J=16.0 Hz, 1H, H-2); δ=8.2 (AB, J=16.0 Hz, H-3); δ=8.1 (d, J=8.0 Hz,
H, H-2′/6′); δ=6.9 (d, J=8.0 Hz, 2H, H-3′/5′); δ=7.6 (d, J=8.0 Hz, 1H, H-3′′); δ=7.8 (m,
2
1
3
H-4′′); δ=8.6 (d, J=8.0 Hz, 1H, H-6′′); 10.6 (bs, 1H, -OH). C NMR (100 MHz, DMSO-d ,
6
ppm): 187.1 (C-1), 126.5 (C-2), 132.4 (C-3), 129.1 (C-1'), 132.0 (C-2'/6'), 115.9 (C-3'/5'),
1
63.1(C-4'), 126.7 and 126.3 (d, JCF =30.0 Hz, C-1''), 164.2 and 161.7 (d, J =255.0 Hz,
CF
C-2''), 117.9 and 117.7 (d, JCF =23.0 Hz, C-3''), 129.5 (C-4''), 125.6, 124.2, 124.1 and
22.9 (dd, JCF =140/120, Hz C-5''), 126.8 (C-6''), 129.1 (-CF ). Poz. LC-MS/MS m/z (%)
1
3
+
+
(
C H F O : 310.06): 333 (100) [M+Na] , 311 (85) [M+1] .
16 10 4 2
2
.1.1.(E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile (5)
Compound 5 was synthesized according to the literature [32]. Yield: 1.74 g (62%). mp:
o
-1
2
02-204 C. IR (KBr pellet), νmax/cm : 3075, 3041 (Ar-H), 2972, 2930, 2866 (Aliph. C-H),
4

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2
1
233 (C≡N), 1588, 1565, 1486, 1412, 1387, 1328, 1268, 1273, 1211, 1165, 1122, 1090,
1
074, 982, 951, 834, 787, 740, 660. H-NMR. (CDCl ), (δ:ppm): 8.20 (d, 1H, Ar-H), 7.88
3
(m, 4H, Ar-H), 7.62 (d, 2H, Ar-H), 7.45 (m, 3H, Ar-H), 7.26 (s, 1H, Ar-H), 6.80 (d, 1H,
1
3
Ar-H). C-NMR. (CDCl ), (δ:ppm): 188.45 (C=O), 163.45 (ArC-F), 156.56 (ArC-O),
3
1
1
1
1
54.70 (ArC-O), 139.44 (C=C), 132.11 (ArC), 129.73 (ArC), 128.66 (ArC), 127.88 (C=C),
27.34 (ArC), 124.68 (ArC), 124.48 (ArC), 123.78 (ArC), 123.55 (ArC), 123.11 (ArC),
22.65 (ArC), 121.94 (ArC), 121.60 (ArC), 121.36 (ArC), 120.83 (ArC), 120.48 (ArC),
20.12 (ArC), 116.46 (C≡N), 118.22 (C≡N). MALDI-TOF-MS, (m/z): Calculated: 436.36;
+
Found: 454.38 [M+H O] .
2
2
.1.2. Synthesis of cobalt (II) phthalocyanine (6)
Compound 6 was synthesized according to the literature [32]. Yield: 272 mg (44%). Mp
o
-1
>
300 C. FT-IR ν /cm (KBr pellet): 3087, 3054 (Ar-H), 2993, 2940, 2861 (Aliph. C-H),
max
1
1
6
556, 1478, 1454, 1430, 1403, 1386, 1361, 1291, 1266, 1245, 1228, 1190, 1087, 1063,
049, 1020, 990, 972, 894, 867, 780, 689. UV-Vis (CHCI ): λmax, nm (log ε): 689 (4.88),
3
18 (4.77), 319 (4.48). MALDI-TOF-MS, (m/z): Calculated: 1804.36;
+
Found:1324.37[M+H O+2H] . C H F N O Cosoluble in CHCl , CH Cl , DMF,
2
96 48
16
8
4
3
2
2
DMSO.
.1.3. Synthesis of copper (II)phthalocyanine (7)
2
Compound 7 was synthesized according to the literature [32]. Yield: 286 mg (44%). FT-IR
-1
νmax/cm (KBr pellet): 3078, 3057 (Ar-H), 2989, 2862 (Aliph. C-H), 1553, 1490, 1487,
1
8
455, 1427, 1399, 1365, 1297, 1276, 1244, 1223, 1178, 1045, 1021, 986, 943, 893, 852,
27. UV-Vis (CHCI ): λmax, nm (log ε): 692 (4.76), 624 (4.58), 324 (4.75). MALDI-TOF-
3
5

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+
MS, (m/z): Calculated: 1808.98; Found: 1829.01 [M+H O+2H] . C H F N O Cu
2
96 48
16
8
4
soluble in CHCl , CH Cl , DMF, DMSO.
3
2
2
3
. Results and discussion
3
.1. Synthesis and characterization
All synthetic routes for (2E)-3-[2-fluoro-5-(trifluoromethyl)phenyl]-1-(4-
hydroxyphenyl)prop-2-en-1-one (3), (E)-4-(4-(3-(2-fluoro-5-
trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile (5) and Co(II) and Cu(II)
(
phthalocyanines (7 and 8) were shown in Figure 1. At the first step of the work (2E)-3-[2-
fluoro-5-(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one (chalcone) was
prepared with the Claisen-Schmidt consendation of 4'-hydroxyacetophenone and 2-fluoro-
5
-(trifluoromethyl)benzaldehyde in basic condition according to known procedure as given
in Figure 1 [33-35]. The purity of chalcone was checked by TLC and its structure was
identified by spectroscopic methods. FT-IR spectra of this compound showed
-
characteristic absorption bands of –OH, C=O and aliphatic C=C groups at 3356 cm 1, 1655
-1
-1
cm and 1569 cm , respectively. The most prominent feature of the structural
characterisation of chalcone compound is the assignment of the proton resonance of its
1
2
α,β-unsaturated moiety, which was done by a careful analysis of its H and D-COSY
3
NMR. From the values of the vicinal coupling constants ( JHα−Hβ = 16.0/16.0 Hz) it was
13
probable to determine the trans configuration of these two protons. C-NMR (APT) also
supported the formation of chalcone with the number of carbon atoms. Moreover in the
1
3
C-NMR, the aromatic and aliphatic carbons containing fluoro atoms appeared as
6

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doublets and doublet of doublet in the region 117.7-164.2 ppm due to C-F coupling. In LC-
+
+
MS/MS spectrum showed [M+Na] and [M+1] fragments as base peaks. Thus, it is seen
that all structural analyzes support the structure.
Second step, the nucleophilic aromatic nitro displacement of (2E)-3-[2-fluoro-5-
(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one with compound 4 was
o
carried out in dry DMF and anhydrous K CO as strong base at 60 C for 72h. (E)-4-(4-(3-
2
3
(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile was obtained with
%
62 yield and characterized with NMR, FT-IR, mass spectral data In the FT-IR spectrum,
.
the
formationof(E)-4-(4-(3-(2-
fluorotrifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile 5 was clearly confirmed by
-1
the disappearance of the -OH band at 3356 cm and appearance of the sharp peak for the -
-1
1
C≡N vibration at 2233 cm . The HNMR spectrum of compound 5 was recorded in
-1
CDCl . The chemical shift of -OH proton in precursor compound 3 at 10.6 ppm
3
disappeared after the formation of dinitrile compound 5. All aromatic and aliphatic protons
13
of compound 5 were observed at between 8.20 and 6.80 ppm. C NMR spectrum of this
compound obviously specified the presence of dinitrile carbon atoms with peaks at 116.46
and 118.22 ppm. In the mass spectrum of compound 5, the expected molecular ion peak
+
was observed at m/z: 454.38 [M+H O] .
2
Peripherally
tetra
(E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy
were prepared by
substituted Co(II) and Cu(II) phthalocyanines 6 and 7
cyclotetramerization reaction using phthalonitrile precursor 5. One of the important
evidence that the cyclotetramerization reaction is taking place is the loss of sharp nitrile
-1
1
13
peak (at 2233 cm ) in the infrared spectrum. The H NMR and C-NMR spectrum of
cobalt and copper phthalocyanine 6 and 7 could not be taken due to the paramagnetic metal
centers [36]. Metal free and metallophthalocyanines are generally insoluble common
7

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organic solvents. However, in this work, thanks to (E)-4-(4-(3-(2-fluoro-5-
(trifluoromethyl)phenyl)acryloyl)phenoxy groups Co(II) and Cu(II) phthalocyanine
complexes 6 and 7 have good solubility in CHCl , CH Cl , THF, DMF.
3
2
2
In the mass spectrum of cobalt and copper phthalocyanines 6 and 7, the presence of
+
+
molecular ion peaks at m/z 1324.37[M+H O+2H] and 1829.01 [M+H O+2H]
2
2
respectively, confirmed the proposed structures.
UV/Vis spectra of the phthalocyanine complexes 6 and 7 show characteristic
*
absorptions in the Q-band region at around 650–700 nm, attributed to the π-π transition
from the HOMO (highest occupied molecular orbital) to the LUMO (lowest unoccupied
-2
molecular orbital) of the Pc ring, and in the B band region (UV region) at around 300–
*
*
4
00 nm, arising from the deeper π-π transitions. The Q-band absorptions of π-π transition
for all phthalocyanines 6 and 7 in CHCl were observed as a single band of high intensity
3
at 689 nm for 4, 692 nm for 5. There was also a shoulder at the slightly higher energy side
of the Q band for each phthalocyanine. B band absorptions of the metallophthalocyanines 6
and 7 were observed at 319, 324 nm respectively (Figure 2).
3
3
.3. Catalytic Studies
.2.1. Oxidation of phenolic compounds with complex 6 and 7
The catalytic properties of Co(II) and Cu(II) phthalocyanine complexes were
investigated for the oxidation of substituted phenolic compounds. All the oxidation
reactions results were given in Tables 2 and 3. All experiments maintained 3 h oxidant and
auxiliary chemicals on the conversion and yields were investigated. Phenolic compounds
can be turned into variety of organic compounds in oxidation reactions. The blank
reactions were carried out (using no catalysts or oxidants) and there were no product
detectable (Table 3). It is proved that presence of the catalyst and oxidant are essential for
the oxidation. The main products was determined as 2,3-dichloro-1,4-benzoquinone and
8

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the side product was determined as 2,3-dichlorobenzaldeyde in the oxidation of 2,3-
dichlorophenol oxidation reaction (Figure 3). Influence of all substrate, catalysts and
obtaining results within the oxidation processes are demonstrated in Table 2. According to
the results of this table, Co(II) phthalocyanine 6 demonstrated the highest activity and
selectivity producing 2,3-dichloro-1,4-benzoquinone as major product in 2,3-
dichloroquinol oxidation reaction. The results of the catalytic oxidation of phenolic
compounds by H O in the presence of 6 are shown in Fig.ꢀ4. This figure showed that 2,3-
2
2
dichlorophenol oxidation reaction has higher total conversion than the other substrates with
catalyst 6.
As the other parameters were kept constant, the molar ratio was carried out in the
range of 300–1000 to determine the influence on substrate to metal ions. The reaction rate
increased with decreasing of the substrate/catalyst molar ratio (Table 3) as expected.
Substrate/catalyst ratio on the oxidation course gave same main product with TON and
TOF values (533 and 177.7 for Co complex 6).
Oxygen activation in oxidation reactions is a challenging problem of modern
chemistry and biochemistry. Co(II) complexes are involved in the one-electron reduction
of oxygen to form the superoxo (Co(III)– ) or peroxo derivatives (Co(III)– –Co(III)) [37-
3
8].
V.N. Shishkin et al reported that the cobalt complex with 4-
octasulfophenyltetrapyrazinoporphyrazine (a ligand with pronounced electron-withdrawing
[
33-
properties) catalyzes the reactions of thiourea and N,N'-dimethylthiourea with oxygen
3
4]
.
The reaction occurs under mild conditions to form the corresponding urea and sulfur in
high yield. In this work, we studied the catalytic oxidation reactions of phenolic
compounds with different oxygen sources and achieved to activate oxygen.
To determine oxygen source effect, H O , TBHP, m-CPBA and air oxygen were
2
2
used as oxidant. The results in Table 2 showed that H O was the best oxidant for 2,3-
2
2
dichlorophenol oxidation in the presence of the CoPc 6. Moreover, TBHP and m-CPBA
can serve as an oxidant but low conversion was observed for both CoPc 6 and CuPc 7. The
reaction color changed from light blue to brown when we added TBHP or m-CPBA in the
reaction media. This clue explains that the complex 6 was degraded immediately with
TBHP or m-CPBA [39-40]. When H O was used as an oxygen source, reaction color was
2
2
bright blue color for 36 minutes and then changed to yellow and light yellow at the end.
This observation proved that phthalocyanine catalyst can be more catalytically active with
H O as an oxygen source in this catalytical process. The results of catalytic activity
2
2
studies for CoPc 6 and CuPc 7 using with air oxygen displayed that there was no formation
9

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of products during the oxidation process (figure 5). To find the optimal reaction conditions,
oxidant/catalyst ratio was tested in 2,3-dichlorophenol oxidation. When the
oxidant/catalyst ratio was increased from 300/1 to 800/1, the rate of the reaction increased.
In contrast, while the catalytic oxidation was processing from 800/1 to 1200/1, the
conversion inclined to decreasing. At this stage, it is possible that the coordination around
the cobalt ion can change and produce inactive intermediate species [41-43].
Temperature effect were also tested as the reaction temperature was upgraded from
o
o
5
0 C to 90 C, the catalytic activity of the CoPc 6 change little bit. When the temperature
ο
was fixed to 50 C, the maximum total conversion was obtained (89%) with cobalt(II)
ο
phthalocyanine 6. Therefore, 50 C is the optimum temperature of 2,3-dichlorophenol
oxidation for product 6 with TBHP in 3 hours. We are interested in the nature of the
introduced transition metals that are used in these catalytic works. Despite
metallophthalocyanines are representatives for flat, π-conjugated carbon systems, their
electronic properties are determined to a large extent by the central metal atom. The
electronic configuration of central metal atom can change the catalytic activity of
phthalocyanine.The activity of metallophthalocyanines in oxidation reaction follows the
order CoPc>CuPc. It is known that the catalytic performance of transition metal species
depends on the outer d-electron density [36].
Changing of the catalyst was monitored by UV–vis spectrophotometer during the
oxidation reaction. Decompositon of Co(II) phthalocyanines is a frequent situation in
oxidation process with the addition of an oxidant [25-31]. Co(II) phthalocyanine in
chloroform has distinctive sharp vibronic Q band due to the monomeric species in the
absence of oxygen source [32]. Before adding oxidant, characteristic sharp Q band of
Co(II) phthalocyanine is seen at 668 nm (Fig. 6). With the oxidation reaction proceeds, this
Q band shifts to 673 nm, broads and disappears at the end of the reaction. Shifting from
6
68 to 673 nm attested that metal oxidation of Co(II)-Pc to Co(III)-Pc [41-43]. After 3 h,
this oxidized intermediate decomposed. Besides, there was no further conversion of any
products. Similar statement can be formed for Fig. 6. As the reaction time progresses,
widenning and disappeararing of Q band are interpreted as in Co(II) phthalocyanine [41-
4
3].
Some reports with Co (II) and Cu(II) phthalocyanine can gain highest turnover
o
number and turnover frequency but at 90 C [27,29,31].When compared with the other
catalysts in the literature, complex 6 and 7 have high TON and TOF value in lower
o
temperature (50 C). The results of our previous work research were also valuble because
1
0

ACCEPTED MANUSCRIPT
of the high conversion and selectivity of Co(II) phthalocyanine. But in this research we are
able to reach the highest product conversion and selectivity with Co(II) phthalocyanine in
o
lower temperature (50 C) for 2,3-dichlorophenol oxidation.
4
. Conclusion
In conclusion, tetra substituted phthalocyanine complexes 6 and 7 bearing (E)-4-(4-
3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy) units were designed and
synthesized. In order to verify these novel products 3–5, a combination of spectral
(
1
13
techniques such as MALDI–TOF mass spectral data, UV–Vis, FT–IR, H NMR and C
NMR was used. MPcs 6-7 are highly soluble in most of the organic solvents and the
catalytic activity of CoPc 6 was examined for the oxidation of 2,3-dichlorophenol using
different oxygen sources. CuPc 7 shows feasible catalytic activity with 72% and 85%
product selectivity for 2,3-dichlorophenol and m-methoxyphenol oxidation. The results
indicated that the catalyst 6 showed convincing activity for the oxidation of 2,3-
dichlorophenol to the corresponding 2,3-dichloro-1,4-benzoquinone as major product in 3
o
hours at 50 C. The optimal conditions were also determined in 2,3-dichlorophenol
oxidation with CoPc 6. All the results indicated that CoPc 6 with catalytic oxidation was an
efficient and cleaning technology for industrial waste application. Converting from
environmentally harmful phenolic compounds into less harmful oxidation products by
CoPc 6 derivative makes this study intriguing.
1
1

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[
2
[
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Table 1. Catalytic activities towards the homogeneous oxidation of phenolic compounds of
some previously reported catalyst.
Catalyst
Substrate
Rxn
Rxn Temp.
Oxidant
Conv.
(%)
Ref.
o
Time
( C)
(
h)
a
CoPcTs
DTBP
TCP
24
24
24
2
70
O2
66
85
67
77
96
[35]
[36,37]
[38]
e
ı
FePc
nr
KHSO5
H O
d
CoPc
a
CoPcTs
2,4,5-TCP
TMP
75
2
2
b
j
FePcTs
nr
O2
[38]
d
CoPc
p-nitrophenol
3
2
90
75
TBHP
TBHP
[39]
[40]
a
CoPcTs
DTBP
61
39
05
b
FePcTs
c
CuPcTs
d
CoPc
DTBP
TCP
3
30
25
TBHP
93
-
[41]
[27]
e
FePc
f
MnPc
97
-
g
CuPc
b
FePcTs
24
H O
24
2
2
1
5

ACCEPTED MANUSCRIPT
h
FePcOC
TCP
10 min
25
H O
6
[42]
[29]
2
2
ı
CoPc
p-nitrophenol
3
90
TBHP
97
75
ı
FePc
a
CoPcTs = Tetrasulfonated cobalt phthalocyanine
FePcTs= Tetrasulfonated iron phthalocyanine
CuPcTs= Tetrasulfonated copper phthalocyanine
CoPc= Substituted cobalt phthalocyanine
FePc= Substituted iron phthalocyanine
b
c
d
e
f
MnPc= Substituted manganese phthalocyanine
g
g
CuPc = Substituted copper phthalocyanine
h
j
FePcOC = Octa cationic iron phthalocyanine
nr= not reported
Table 2. Oxidation of Substituted Phenols Catalyzed by Complex 6 and 7.
Substrate
Major Product
Total
Conversion
Product
Selectivity
(%)
TON
TOF
(h )
-
1
(
%)
6
7
6
7
6
7
6
7
OH
O
5
1
50
32
26
305
299
101.6 99.8
NO2
OH
O
O
Cl
Cl
75
89
68
72
59
80
90
75
85
72
66
449
533
473
407
431
353
149.8 135.8
177.7 143.8
157.8 117.8
O
O
OH
Cl
Cl
Cl
Cl
O
OH
O
7
9
O
OCH3
OCH3
TON = mole of product / mole of catalyst
TOF= mole of product / mole of catalyst x time
Conversion was determined by GC.
Catalyst/substrate/oxidant ratio=1/600/800, Reaction Time=3 hours.
1
6

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Table 3. Selective oxidation of 2,3-dichlorophenol with catalysts 6 and 7 using different
oxidant and temperature.
a
-1
Subs./Ox./Cat
Oxidant
H O
Temperature
Conversion (%)
Selectivity (%)
TON
TOF (h )
6
65
o
(
C)
6
7
6
7
6
7
7
50
3
6
00/800/1
00/800/1
50
50
65
89
50
72
54
90
46
72
195 150
2
2
2
H O
2
533 431 177.7 143.8
9
00/800/1
H O
50
50
50
50
50
50
50
50
75
90
25
50
50
74
70
62
70
55
49
37
-
89.6
79
61
-
66
54
45
57
45
39
28
-
47
45
31
-
78
86
65
77
59
50
60
-
90.9
88
51
-
57
49
70
63
47
45
41
-
68
59
39
-
666 594
840 648
372 270
360 342
330 270
294 234
222 162
222
280
124
120
110
98
74
-
179
198
216
90
114
90
78
54
-
94
90
62
-
2
2
2
2
2
2
1
200/800/1
H O
2
6
00/300/1
00/500/1
00/1200/1
H O
2
6
6
H O
2
H O
2
6
6
6
6
6
6
00/800/1
00/800/1
00/800/1
00/800/1
00/800/1
00/800/1
m-CPBA
TBHP
Air oxygen
H O
-
-
537 282
474 270 158
366 186 122
2
2
2
2
2
2
H O
2
H O
2
6
00/800/free cat.
00/free ox./1
H O
-
-
-
-
-
-
2
6
H O
2
-
-
-
-
-
TON = mole of product / mole of catalyst
TOF= mole of product / mole of catalyst x time
Conversion was determined by GC.
-3
-3
-6
Reaction Conditions: 600/800/1: 1.66×10 mol)/ 2.22×10 mol/ 2.77×10 mol
a
=
Selectivity of TMHQ Reaction time=3 hours.
1
7

ACCEPTED MANUSCRIPT
Figure Captions
Figure 1. Synthesis of precursor phthalonitrile compound 3 and MPcs 6 and 7 Reagents
and conditions: (i) dry DMF, K CO , 60°C, 96 h; (ii) n-pentanol, DBU, 160 °C, CoCl ,
2
3
2
CuCl2.
-5
Figure 2. UV–Vis spectra of 1.00 x 10 M of complexes. (a) Co(II)Pc, Cu(II)Pc in CHCl .
3
Figure 3. The oxidation products of 2,3-dichlorophenol.
Figure 4. Time‐ dependent conversion of phenolic compounds oxidation with H O as an
2
2
oxidant for catalyst 6
Figure 5. The oxidant effect on 2,3-dichlorophenol oxidation [Reaction conditions: 2,3-
-3
-6
-3
dichlorophenol (1.66x10 mol), Co(II)Pc and Cu(II)Pc (2.77x10 mol), oxidant (2.22x10
o
mol), DMF (0.01 L), 3 hours and 50 C].
Figure 6. Time-dependent changes in the visible spectrum of the oxidized complex 6
-
3
-
observed on addition of TBHP (2.22x10 mol) to a reactio mixture containing 1.66 x10
3
-6
mol 2,3-dichlorophenol and 2.77 x10 mol complex 6 catalyst in 10 ml: (e) 36 min; (d) 72
min; (c) 108 min; (b) 144 min (a) 180 min after addition of TBHP. All spectra for the
oxidized complex 6 were taken after sixfold dilution with acetonitrile. (f) Visible spectrum
of (non-oxidized) complex 6 in DMF.
1
8

ACCEPTED MANUSCRIPT
1
9

ACCEPTED MANUSCRIPT
O
O
F
O
F
2
'
3
2''
1
'
1''
3
''
H
3'
1
i
2
6
'
HO
6''
4''
HO 4'
5
''
5'
3
CF3
1
2
CF3
ii
CN
CN
O N
2
O
F
4
NC
NC
O
5
CF3
iii
R
R
N
O
F
N
N
N
N
M
N
R= O
N
CF3
N
M: Co and Cu
and 7
R
R
6
Figure 1. The synthesis of cobalt and copper phthalocyanines. Reagents and conditions:
i)NaOH, EtOH/H O, stirring at room temperature for 24 h, 0.1N HCl for pH 6 (ii) dry
(
2
DMF, K CO , 60°C; (ii) n-pentanol, DBU, 160 °C, CoCl , CuCl .
2
3
2
2
2
0

ACCEPTED MANUSCRIPT
2
1
.5
1
0
.5
2
00
300
0
400
500
600
Wavelength ( nm )
Figure 2. UV-Vis Spectrum of complex 6 with red color and complex 7 with black color
700
800
900
2
1

ACCEPTED MANUSCRIPT
Figure 3. The oxidation products of 2,3-dichlorophenol.
2
2

ACCEPTED MANUSCRIPT
Figure 4. Time‐ dependent conversion of phenolic compounds oxidation with H O as an
2
2
oxidant for catalyst 6
2
3

ACCEPTED MANUSCRIPT
Figure 5. The oxidant effect on 2,3-dichlorophenol oxidation [Reaction conditions: 2,3-
-3
-6
-3
dichlorophenol (1.66x10 mol), Co(II)Pc and Cu(II)Pc (2.77x10 mol), oxidant (2.22x10
o
mol), DMF (0.01 L), 3 hours and 50 C].
2
4

ACCEPTED MANUSCRIPT
Figure 6. Time-dependent changes in the visible spectrum of the oxidized complex 6
-
3
-
observed on addition of TBHP (2.22x10 mol) to a reactio mixture containing 1.66 x10
3
-6
mol 2,3-dichlorophenol and 2.77 x10 mol complex 6catalyst in 10 ml: (e) 36 min; (d) 72
min; (c) 108 min; (b) 144 min (a) 180 min after addition of TBHP. All spectra for the
oxidized complex 6 were taken after sixfold dilution with acetonitrile. (f) Visible spectrum
of (non-oxidized) complex 6 in DMF.
2
5

ACCEPTED MANUSCRIPT
►
Synthesis of (E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted
Co(II) and Cu(II) Phthalocyanines ► Determination of catalytic activities of Co(II) and
Cu(II) phthalocyanines on oxidation of phenols.► Different parameters influenced the
oxidation process were determined.