Copper nanoparticles supported on highly nitrogen-rich covalent organic polymers as heterogeneous catalysts for the ipso -hydroxylation of phenyl boronic acid to phenol

Article abstract of DOI:10.1039/c9nj05759e

This work describes a simple procedure for the synthesis of highly nitrogen-rich covalent organic polymers using commercially available starting materials like melamine and cyanuric chloride as a solid heterogeneous catalyst Cu/TCOP under solvothermal conditions. The structural properties of the as-synthesized solid heterogeneous catalyst were determined by X-ray diffraction (XRD), diffuse reflectance spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), ¹³C-CP MAS nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. The catalytic activity of Cu/TCOP was investigated by focusing on the oxidation of phenylboronic acid under atmospheric conditions in an aqueous medium, achieving a very good yield up to 99%. The reaction performance was evaluated considering the effect of various parameters, such as the amount of the catalyst, reaction time, temperature, and the amount of the base and solvent. The Cu/TCOP catalyst is completely recoverable in a facile manner from the reaction mixture and the efficiency of the copper nanocatalyst can be recovered after five cycles.

Full text of DOI:10.1039/c9nj05759e

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Copper nanoparticles supported on highly nitrogen‐rich containing covalent organic
polymers as heterogeneous catalyst for ipso-hydroxylation of phenyl boronic acid to
phenol
b
Muniyasamy Harikrishnan,a Ganesan Elamathi,a Rajendran
Velu Sadhasivam,
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Balasaravanan, Sepperumal Murugesan and Ayyanar Siva*
aSupramolecular and Organometallic Chemistry Lab, Department of Inorganic Chemistry,
School of Chemistry, Madurai Kamaraj University, Madurai-625 021, Tamil Nadu, India.
bDepartment of chemistry, V. M. K. V Engineering College, Vinayaga Mission's Research
Foundation (Deemed to be university), Salem, Tamil Nadu, India.
E-mail: drasiva@gmail.com (Ayyanar Siva)
Abstract
This work describes a simple procedure for the synthesis of highly nitrogen‐rich
containing covalent organic polymers using commercially available starting material like
melamine and cyanuric chloride as a solid heterogeneous catalyst Cu/TCOP under
solvothermal conditions. The structural properties of the as-synthesized solid heterogeneous
catalyst were determined by X-ray diffraction (XRD), diffused reflectance spectroscopy,
Fourier transformed infrared (FT-IR) spectroscopy, field emission scanning electron
microscopy (FESEM), energy dispersive X-ray spectroscopy(EDS), 13C-CP MAS nuclear
magnetic resonance spectroscopy and X-ray photo electron spectroscopy. The catalytic
activity of Cu/TCOP was investigated by focusing on oxidation of phenylboronic acid under
atmospheric conditions in aqueous medium to get very good yield up to 99%. The reaction
performance has been evaluated considering the effect of various parameters such as amount
of catalyst, reaction time, temperature, amount of base and solvent. The Cu/TCOP catalyst is
completely recoverable in a facile manner from the reaction mixture and the efficiency of the
copper nano catalyst was recovered for after five cycles.
1
. Introduction
Over the past few decades, there has been an exponential improvement in the number
of papers was published in synthesis of covalent triazine based porous polymeric materials,
such as covalent-organic framework (COF), covalent triazine polymers (CTPs). These
materials are a new class of highly nitrogen rich containing porous crystalline materials,
1

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CTPs are composed of lightweight elements C, N and O to forming a strong covalent bonds
linked to generate a two- and three- dimensional (2D and 3D) polymeric network structures.1,
2
These type of nitrogen rich polymeric materials have attracted and great attention in current
research areas and CTPs have tailored to specific functional applications including gas
adsorption studies like carbon dioxide, methane, hydrogen storages.3-5 Nevertheless, recently
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solar cells,11,12
expanded to sensors, drug delivery, optoelectronics, water splitting,
energy storage,13 proton conduction,14 gas separations15,16 photocatalyst17 and more
substantially used for heterogeneous catalysis applications,18,19 In most of the cases
homogeneous phosphines based ligands were used for catalytic reaction, such as PtBu3,
PCy , biphenyl-based phosphines,
phosphapalladacycles, hemilabile phosphines and
3
ferrocene phosphines are employed as ligands. Despite considerable success, the major
drawbacks associated with such phosphines are their moisture sensitivity, handling problems,
high cost, synthetic difficulties, inherent toxicity and environmental hazards etc. In this
situation, nitrogen enrich containing solid supports are generally advantageous for catalytic
reaction and they are easy-to-handled, less expensive than their phosphine counterparts,
hazards free, usually stable to air/moisture, etc. In addition to that CTPs have highly ordered
structures, well-defined and tunable porous nanochannels. During the last two decades,
imine-based CTPs have been extensively studied for heterogeneous catalyst application,20
because of the CTPs have some more advantages compared to other solid supported materials
2
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such as metal organic frame works (MOFs), silica (SiO ) and graphene. The CTPs have
2
high surface area, low density, crystalline, permanent porosity, highly stable in thermal
treatment with water and some common high boiling organic solvents. Moreover, large
amount of nitrogen atom enriched in this CTPs networks, which is beneficial to incorporate a
large number of metal binding sites; hence the surface of solid supported material to enhance
the high catalytic activity as well as high stability. In our previous studies, we have
successfully synthesized and reported triazine-based covalent organic polymers as novel solid
supports for incorporated palladium NPs as a heterogeneous catalyst for Suzuki-Miyaura
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(Csp -Csp ), Mizoroki-Heck (Csp -Csp ) and selenium insertion of aryl halide (Csp -Se)
coupling reactions. were studied.22-24
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OH
OH
HO
O
O
OH
OH
OH
Carvacrol
Anti-bacterial)
Thymol
Kaempferol
Anti Oxidant)
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(
(Antiseptic)
(
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Resveratrol
Anticancer)
(
+)-Catechin
(
(Anti Oxidant)
HO
O
a-Tocopherol
Vitamin-E, Anti Oxidant)
(
Figure 1. Structure of phenolic compound used in late clinical research.
In recent years, transition metal catalyzed cross coupling reactions such as C-C, C-N,
C-O, C-Se bond formation reactions have achieved considerable progress in synthetic organic
transformations, pharmaceutical and medicinal applications.25, 26 Cu-catalyst were used in
performing the hydroxylation of phenyl boronic acid to corresponding aryl alcohol have
achieved considerable progress in synthetic organic transformations, these type of phenol or
substituted phenol are most important methods for preparing arylated ether, which are key
intermediates for the synthesis of natural products, pharmaceutical drugs, perfumes industries
(
Figure 1). Furthermore, the functionalized aromatic alcohols and phenols which are widely
used as an important intermediate in dyestuffs, agro chemicals, ligands, schiff base metal
complex, additives, conducting polymers, pesticides, and pharmaceutical products.
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NH2
N
HN
HN
N
N
N
N
N
N
N
H N
N
NH2
2
NH
HN
N
N
NH
Cu
HN
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NH
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Melamine
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Cu
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Cu(NO ) . 3H O
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N2H4.H2O
HN
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N
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Cl
HN
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NH
o
H
o
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0 C/48 h
60 C
H
N
N
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N
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HN
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NH
Cl
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Cl
HN
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Cyanuric chloride
TCOP
Cu/TCOP
Cu - Cu NPs
Scheme 1. Synthesis of Cu NPs supported on nitrogen rich covalent triazine polymer
networks (Cu/TCOP).
In this work, we report here, the synthesis and characterization of a novel Cu NPs
supported on highly nitrogen containing triazine polymer (Scheme 1) as a solid
heterogeneous catalyst (Cu/TCOP) have been used to carried out the oxidation of phenyl
boronic acid using H O as an oxidant in Ethanol/water (1:1) ratio solvent for about 20 min
2
2
without any other additives (acids or base) and thoroughly investigated (Scheme 2). Some of
the researchers are successfully carried out this type of oxidation reaction but using strong
oxidizing agent and metal salts for stoichiometric amount and high temperature. To the best
of our knowledge, there are no reports describing the Cu/TCOP as a heterogeneous catalyst to
utilize oxidation of phenyl boronic acid under room temperature.
HO
OH
OH
B
H O
2
2
Cu/TCOP
R
R
Scheme 2. Synthesis of phenols from hydroxylation of phenyl boronic acid for oxidation
reaction.
2. Experimental sections
2
.1. Materials and methods
All the chemicals and reagents were purchased from commercial reagent suppliers,
used without further purification as commercially available unless otherwise noted. All the
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DOI: 10.1039/C9NJ05759E
solvents were obtained from laboratory reagent grade. The H and C NMR spectra were
recorded on a Bruker (Avance) 300 and 400 MHz NMR instrument using TMS as an internal
standard and CDCl as a solvent. Chemical shifts are given in ppm (δ-scale) and the coupling
3
1
3
constants are given in Hz. C CP-MASNMR was recorded using a Burker Avance 500 MHz
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operating at 75 MHz for C nuclei. Powder X-ray diffraction (PXRD) patterns were obtained
o
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on a Rigaku diffractometer using CuKα ( =1.5404 Å) source with a scan rate of 0.5 min .
The morphology and particle size of the polymerized materials were examined by SEM and
TEM. The scanning electron microscopy (SEM) measurements were performed by VEGA3
TESCAN, CZECH REPUBLIC. Energy dispersive X-ray spectroscopy (EDX) was carried
out using Bruker Nano, Germany. The FT-IR spectra were obtained from a JASCO FT/IR-
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10 spectrometer. Silica gel-G plates (Merck) were used for TLC analysis with a mixture of
n-hexanes and ethyl acetate as an eluent. Column chromatography was carried out on silica
gel (60-120 mesh) using n-hexanes and ethyl acetate as an eluent.
2.2. Synthesis of TCOP polymer
In a typical synthetic procedure a 100 mL Schlenk tube was charged with
melamine (300 mg, 2.37 mmol) and cyanuric acid (570 mg, 3.09 mmol) were dissolved in a
50 mL (1:2) of dioxane/DMSO mixture, and stirred well under nitrogen atmosphere.
Generally melamine doesn’t soluble in normal solvent, the solubility of melamine and
cyanuric acid was very limited so we can use DMSO as solvents for this polymeric reactions.
Furthermore, the resultant homogeneous solution was treated with K CO and then colorless
2
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homogeneous solution was appeared. The reaction vessel was capped tightly and then
transferred to oil bath which is maintained at a temperature 90 °C for about 2 days, colorless
solid was observed. After completion of the reaction, the mixture was poured into a 50 mL
of water and stirred for 2 h, the colorless solid was completely settled in the bottom of
aqueous solution. After that, the colorless solid was filtered and subsequently washed several
time with DMF, THF, acetone, DCM and DMSO to remove the unreacted starting materials.
Finally, the solid was soaked into acetone and water for one day and filtered, then dried at 80
°C under vacuum oven for 8 h to get 80% yield of colorless solid product. FT-IR (powder
-1
cm ) 3362, 3210, 1649, 1617, 1472, 1295, 1200, 1124, 107, 1023, 846, 758, 624, 574, 524.
Elemental analysis calculated from EDS analysis (Atomic %) for C 49.74, N 24.00, O 15.89,
(
Si 6.45, Mg and Ca 1.72, Na 2.27) these TCOP materials were coated in glass plates, Si, Mg,
Ca and Na all are glass plates chemical components.
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2
.3. Synthesis of Cu/TCOP polymer
To a 100 ml round bottom flask was added subsequently colorless solid TCOP (100
mg) was dispersed into methanol (15 mL) and Cu(NO ) . 5H O (20 mg) was added into the
3 2
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reaction mixture then stirred at room temperature for 30 minutes, After that, the reducing
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stirred for about 6h, and then filtered, washed with several time methanol (3 × 20 mL),
acetone (3×20 mL) and water to remove the unreacted Cu(NO ) .5H O. Finally, the solid
3 2
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was dried in a vacuum oven at 70 °C for 8 h to obtain Cu/TCOP as a light brown colored
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powder (93 mg, 93% yield). FT-IR (powder cm ) 3381, 1566, 1421, 1345, 1213, 1130, 1023,
852, 751, 75, 612, 536. Elemental analysis calculated from EDS analysis (Atomic %) for C
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2.76, N 25.17, O 19.11 and Cu 0.71. From the ICP-AES analysis 0.121 wt% of copper
content is presented in the Cu/TCOP materials. These results are more are less equally
matched with EDX spectra
2
.4. General reaction procedure for oxidation of phenyl boronic acid to phenol
Phenyl boronic acid (1 mmol), hydrogen peroxide H O (1 mmol), Cu/TMCP (20 mg)
2
2
were taken in DMF solvent and the reaction mixture was stirred at room temperature for
about 20 minutes. After completion of the reaction (monitored by TLC), the reaction mixture
was diluted with 5 mL ethyl acetate and then the catalyst was removed by simple filtration
using whatt man 40. The filtrate solution was washed with brine and extracted with an excess
amount of ethyl acetate and then concentrated under reduced pressure. Finally, the crude
product was further purified by silica gel (60-120 mesh) column chromatography (petroleum
ether/ethyl acetate) to afford the corresponding phenols and tiny amount of homo coupled
byproduct was observed.
3
3
. Result and Discussions
.1. Characterization of TCOP and Cu/TCOP
The triazine containing nitrogen enriched covalent organic polymers (TCOP) were
successfully synthesized by the nucleophilic substitution reaction between melamine and
cyanuric chloride then mixture of DMSO and 1,4-dioxane (1:1) at 90 ºC for about 48 h under
solvothermal conditions. Furthermore, the Cu NPs successfully incorporated to the TCOP
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polymeric materials using Cu(NO ) . 5H O metal precursor and hydrazine monohydrate as
DOI: 10.1039/C9NJ05759E
3
2
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reducing agent to get light grey color heterogeneous solid materials (Cu/TCOP).
(a)
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C-Cl
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C=N *
(N-H)
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Cu/TMCP
3rd Recycle catalyst
Cyanuric chloride
Melamine
(-NH )
2
TMCP
500
1000
1500
2000
2500
3000
3500
4000
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1000 1500 2000 2500 3000 3500 4000
Wavenumber (cm-1)
Wavenumber (nm)
Figure 2. FT-IR Spectra of compounds (a) melamine, cyanuric chloride and TCOP; (b)
rd
Cu/TCOP and 3 recycle catalyst.
The FT-IR spectra of triazine containing nitrogen enriched covalent organic polymer
TCOP and Cu/TCOP are shown in figure 1. Further, the observation of only broad stretching
-1
vibration band was observed at 3347 cm (instead of multiple bands observed for primary
amine group for melamine) in the FT-IR spectrum [Figure 2a] along with the obvious
-1
consumption of strong stretching vibration bands of C-Cl at 847 cm was observed for
triazine containing polymeric materials TCOP compared with starting material, which
suggested that the successfully conversion of all the starting material of melamine and
cyanuric chloride into TCOP polymer through aminal linkage to form three dimensional
network polymers. Furthermore, the TCOP and Cu/TCOP both materials show similar
stretching bands was observed, but the C=N stretching band for triazine ring Cu/TCOP shows
-1
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5 cm slightly blue shifted, its attributed to Cu nanoparticle successfully incorporated into
the polymeric network (Figure 2b). In addition, the Cu/TCOP and reusable catalyst does not
show any different for absorption position, it is clearly indicated that the structural regularity
was well maintained during the course of reactions. 27-29
The optical properties and metal binding sites were confirmed by Solid state UV-
Visible spectroscopy is an effective technique, whether the metal salts are completely
reduced in to metal NPs. The absorption spectra of both the TCOP and Cu/TCOP shows that
the two characteristic absorption band appeared at 220 nm and 245 nm, which may be
attributed to π-π* and n-π* transition of C= N, C-N respectively, which are represented in
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Figure 3. Further, Cu/TCOP showed the new broad absorption band appeared at near 558-730
nm, which is due to the charge-transfer transitions of an electron excited from the triazine
nitrogen lone pair to vacant d-orbitals of the metallic nanoparticles. Hence it is clearly
revealed that all Cu NPs are successfully incorporated on nitrogen-rich containing TCOP
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networks 30, 31
2.0
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TCOP
Cu/TCOP
rd
3
recycle catalyst
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Wavelength (nm)
rd
Figure 3. UV- DRS spectra of compound TCOP, Cu/TCOP and 3 recycle catalyst.
The crystalline nature and structural regularity of both TCOP and Cu/TCOP were
determined by powder XRD analysis which is shown in Figure 4. The obtained powder XRD

pattern TCOP shows partial crystallinity of the material, due to the range of 14 to 32 and
4
2.72 2 values. This set of broad peaks suggests that TCOP material has a certain degree of
order.32, 33 The comparison of TCOP and Cu/TCOP revealed that TCOP was well maintained
after the synthesis of Cu/TCOP, because of these both materials have similar patterns was
observed. It is also confirmed by FTIR spectrum, but the Cu/TCOP additionally new small
peak was observed in these 2 values at 11.52, 15.70, 20.43, 24.79, 26.97, 35.30 and
4
2.29 which are assigned to the Cu NPs strongly binding/interaction with triazine unit as
well π-π stacking between aromatic ring and triazine unit to form certain degree of order,
which is consistent with our reported literature. 34-36
8

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TMCP
8
7
6
5
0
0
0
0
*
*
Cu/TMCP
*
rd
3
Recycle catalyst
*
*
*
*
* Cu NPs
*
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
40
30
20
20
40
60
80
2
Theta
rd
Figure 4. Powder XRD pattern of TCOP, Cu/TCOP and 3 recycle catalyst.
The architecture of TCOP and Cu/TCOP was further evaluated at the molecular level
1
3
by C{H}-Cross Polarized-Magic Angle Spinning (CP-MAS) NMR spectra (Figure 5). The
TCOP materials shows two characteristic strong signals were observed at around 166.12 and
154.91 ppm, respectively. This is attributed to the carbon of the triazine ring and another peak
1
54.91 ppm it may be attributed to the terminal unit, side group functionalities originated
from cyanuric chloride. Further we confirmed that, melamine and cyanuric chloride
successfully incorporated by nucleophilic substitution reaction into the triazine containing
nitrogen enriched covalent organic polymeric materials (TCOP) through aminal linkage.
HN
N
N
N
N
NH
HN
N
N
H
N
N
N
HN
N
N
N
NH
H
N
HN
N
NH
Figure 5. CP-MAS NMR spectrum of compound TCOP.
9

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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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The oxidation state of Cu2p and chemical environment of molecular structure, bond
nature of the solid supported material TCOP were analysis by using high resolution X-ray
Photoelectron Spectroscopy (XPS) results are presented in Figure 6. The Cu/TCOP binding
energy values appeared at 936.20 eV and 956.6 eV is assigned to Cu2p3/2 and Cu2p1/2,
respectively. The copper nanoparticle is presented in Cu(II) oxidation state in the form of
CuO. The Cu/TCOP binding energy values appeared at 936.20 eV and 956.6 eV is assigned
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
+
to Cu2p3/2 and Cu2p , respectively. This corresponds to Cu species present in the Cu
1/2
oxidation state in the form of CuO NPs. Further, the free Cu2+ in copper nitrate salt in
Cu2p3/2 and Cu2p1/2 peaks appeared at 935.30 eV and 955.70 eV was observed in
literatures, compared with our obtained binding energy values slightly negative shift was
observed, which clearly indicates that copper oxide NPs are strongly interacting with imine
nitrogen species in Cu/TCOP. In addition to that, the small binding energy value was
observed at 945.21 eV and 964.03 eV, respectively, which is corresponding to Cu2p3/2 and
Cu2p1/2 satellite peaks. In order to investigate, the N1s spectra (Figure 5a) shows that binding
energy values appeared at 400.01 eV and 401.1 eV, which is attributed to -C=N-C core
triazine imine nitrogen and secondary amine functionalities (N-H) of triazine solid supports
(TCOP). The imine nitrogen unit N 1s core level was previously reported at 398.80 eV. 37-39
The observed nitrogen N 1s core level binding energy at 400.01 eV, which was slightly
positive shifted the imine units N1s core level of the Cu/TCOP. These results clearly
suggested that the copper oxide NPs are strongly interacting with imine nitrogen species in
Cu/TCOP. These observed results are matched with pervious reported literatures, finally, the
CuO NPs strongly supported with core triazine nitrogen.40, 41 In addition, the O1s and C1s
core level binding energy level was included in figure S1 and S2 see SI.
6000
5000
4000
3000
4000
3500
3000
2500
2000
1500
(b)
(a)
Cu 2p3/2
Cu/TCOP
Cu2p1/2
N1s
N-H
Core triazine
C=N
sat.peak
-
sat.peak
2000
1000
930
940
950
960
396
398
400
402
404
406
408
410
Binding Energy (eV)
Binding Energy (eV)
1
0

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3
0000
(C)
Cu/TCOP
25000
N1s
O1s
N1s
20000
15000
10000
C1s
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
000
0
200
400
600
800
1000
Binding Energy (eV)
Figure 6. XPS analysis of (a) Cu2p and (b) N spectra of Cu/TCOP.
1
S
Figure 7. SEM images of compound (a) TCOP (b) Cu/TCOP.
1
1

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1
1
1
1
1
1
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1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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0
1
2
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4
5
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 8. TEM images of compound Cu/TCOP.
In order to investigate the morphological structure of the solid supports TCOP and
catalyst Cu/TCOP was confirmed by scanning electron microscopy (SEM) and Transmission
electron microscopy (TEM) are shown in Figure 7 and 8. The SEM images of TCOP and
Cu/TCOP materials showed direct visualization of porous cross-linked polymeric structure
and smooth surface with partially crystalline nature and TEM images of morphology
structure of Cu/TCOP catalyst shows CuO NPs dispersed into the surface of the TCOP
polymeric supports, the black dots are represented as CuO NPs, the average particle size is
2
.29 nm.
Table 1. Optimized reaction condition of phenyl boronic acid to phenol for oxidation
reactions.
HO
OH
B
OH
Oxidizing agent
Catalyst,Solvent
1
2

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Entry
Catalyst
Solvent
Hydrogen
source
Temp Time
Yield
(°C)
(min)
(%)
NR
NR
98
1
2
3
4
5
6
-
EtOH/H O
H O
Rt
10
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
TCOP
EtOH/H O
H O
2
Rt
10
2
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu/TCOP
EtOH/H O
H O
2
Rt
10
2
EtOH/H O
O2
Rt
10
NR
90
2
EtOH/H O
TBHP
Rt
10
2
EtOH/H O
Benzoyl
peroxide
Rt
10
70
2
7
8
9
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu/TCOP
Cu(OAc)2
CuI
THF
H O
Rt
Rt
Rt
Rt
Rt
Rt
Rt
Rt
Rt
10
10
10
10
10
10
10
10
10
79
90
90
95
62
68
50
47
52
2
2
2
2
2
2
2
2
2
2
MeOH
H O
2
H O
2
H O
2
1
1
1
1
1
0
1
2
3
4
MeOH/H O
H O
2
2
Toluene
DMF
-
H O
2
H O
2
H O
2
EtOH/H O
H O
2
2
15
EtOH/H O
H O
2
2
Reaction condition: Phenyl boronic acid (1 mmol), H O (1.5 mmol), H O/Ethanol solvent
2
2
2
(
1:1 ratio, 2 mL), catalyst (15 mg of Cu/TCOP 0.115 wt% and 0.01817 mol% of copper
present), 10 min.
Initially, we have been synthesized nitrogen enriched porous triazine polymers
Cu/TCOP to determine the potential catalytic activity of heterogeneous catalyst in oxidation
of phenyl boronic acid to get corresponding phenols, using different oxidation sources in
1
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1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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various solvents with different amount of catalytic Cu/TCOP was investigated, the observed
results are shown in Table 1. Herein, we can choose phenyl boronic acid was used as a model
substrate and hydrogen peroxide (H O ) as a oxidation source in the presence of a catalyst to
2
2
optimize the reaction conditions at room temperature. As expected, no reaction was observed
either in the presence of TCOP or absence of catalyst Cu/TCOP) (Table 1, entries 1, 2).
Hence, the Cu/TCOP catalyst plays a vital role for the oxidation of phenyl boronic acid and
the solid supports does not involve in the catalytic reaction. In addition, the effect of different
oxidant, phenyl boronic acid to corresponding alcohols oxidation reaction were performed in
various oxidant such as O , benzoyl peroxide, TBHP, NaOCl and H O , the efficiently
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
2
2
oxidation reaction was performed by H O compared with other oxidant (Table 1, entries 3-
2
2
6
). H O was a mild oxidant choice because it only produces water and oxygen hazards free
2 2
and harmless one. Moreover, no product was obtained either in the presence of molecular O2
(Table 1 entries 4), Furthermore, this oxidation reaction was optimized with various solvent
like toluene, DMF, water, methanol, ethanol, ethanol/H O and THF, ethanol/H O obtained
2
2
major amount of yield compared with other solvent system due to ethanol/H O more polar
2
protic solvents and high dielectric constant as well highly soluble in organic substrate.
Finally, the oxidation reaction optimized with various copper based metal precursor such as
CuCl , CuI and Cu(OAc) to give less amount of yield 52%, 47% was observed; so the CuO
2
2
NPs was effectively performed in this reaction (Table 1, entries 14, 15)
The identified above optimized reaction conditions after go the substrate scope for
oxidation of phenyl boronic acid and hydrogen peroxide (H O ) as a oxidation source in the
2
2
presence of a catalyst, EtOH/H O (1:1) solvent at room temperature, we then studied variety
2
of substituted phenyl boronic acid (Table 2), the substrates containing both electron-rich and
electron-poor groups were tolerated well and provide the corresponding phenol in moderate
to good yields was observed. In addition, the reaction was performed pyridine 3-boronic acid
to obtained 40% of yield was observed; due to the substrate pyridine was coordinated to Cu
nanoparticles the catalyst active site was deactivated, so the yield was obtained moderately
(
Table 2 entry 5). The yield was totally reduced 99%, 80% and 65% was observed, when the
reaction was carried out phenyl boronic, napthyl 1-boronic acid and pyrene 1-boronic acid,
increasing the number of rings in the substrate to reduce the amount of yield; due to the
increasing hydrophobic nature, less solubility and bulky molecules and large substrate does
not penetrate into the porous catalytic site of the Cu/TCOP porous materials. (Table 2, entries
1
, 7 and 8), Furthermore, the sterically hindered substrates 2-clhoro phenyl boronic acid,
1
4

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pyridine 3-boronic acid and o-nitro phenyl boronic acid tocorresponding aromatic alcohol
products in moderate amount of yields was observed (Table 2, entries 9, 12).
Table 2.Water/Ethanol (1:1) mediated Phenyl boronic acid to Phenol oxidation reaction
catalyzed by Cu/TCOP with various substituents.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
HO
OH
R
B
OH
H O
2
2
EtOH/H O
Cu/TMCP, rt
2
R
Entry
Aryl boronic
acid
Product
Temp.
Time
Yield
(%)
(°
C)
(min)
OH
B(OH)2
1
2
3
rt
rt
rt
10
99
92
82
B(OH)2
OH
OH
H3C
20
B(OH)2
OHC
OHC
20
B(OH)2
OH
4
5
OHC
OHC
Rt
30
30
80
40
F
F
B(OH)2
OH
N
rt
N
1
5

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9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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B(OH)2
B(OH)2
OH
6
7
rt
40
20
87
CN
CN
OH
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
35
80
B(OH)2
OH
8
9
40
rt
20
25
20
65
70
85
B(OH)2
NO2
OH
NO2
1
0
B(OH)2
OH
rt
H COC
3
H COC
3
1
1
1
2
B(OH)2
OH
rt
rt
20
30
90
77
NC
NC
B(OH)2
Cl
Cl
OH
1
1
3
4
B(OH)2
B(OH)2
OH
rt
rt
20
20
87
85
MeO
Br
MeO
Br
OH
Reaction condition: Phenyl boronic acid (1 mmol), H O (1.5 mmol), H O/Ethanol solvent
2
2
2
(1:1 ratio, 2 mL), catalyst (15 mg of Cu/TCOP 0.115 wt% and 0.01817 mol% of copper
present), 10 min.
1
6

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In order to investigate the kinetic study of the heterogeneous Cu/TCOP catalyst in our
optimal reaction condition, the obtained results are shown in figure 9. The oxidation reaction
was carried out phenylboronic acid and H O oxidant DMF/H O as solvent at ambient
2
2
2
temperature, this reaction was completed within 25 min and each five minutes time intervals
the product conversion was observed at 0%, 38%, 65%, 88% 96% and 98% (Figure 9).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
100
8
0
0
Cu/TCOP catalyst
6
40
20
0
0
5
10
15
20
25
Time (min)
Figure 9. Effect of reaction time on the percentage conversion of bromobenzene catalyzed by
Cu/TCOP for oxidation reactions
Further, we compared the oxidation reaction in the presence Cu/TCOP and other
reported solid support materials, the results are given in Table 3. From the table, we observed
that our synthesized triazine based catalytic system (Cu/TCOP) is best for oxidation of
boronic acids when compared to other catalytic system.
1
7

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1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
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Table 3. Previously reported catalytic performance of different transition metal-based
catalyst for hydroxylation of phenyl boronic acid with different oxidants.
S.No
Catalyst
solvents
Oxidant
Time
(min)
Temp Yield
Ref
o
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
( C)
(%)
1
2
3
Pd/bentonite NPs
Ru[(bpy) Cl ]
H O
H O
60
28 h
8h
rt
94
[42]
[43]
[44]
2
2
2
DMF
Ellagic acid
MeOH
O2
rt
81
3
2
CuSO .5H O
O2
60
91
4
2
4
5
6
7
8
9
PhI(OAc)2
AgNPs-K10
Cellulose
MeCN: H O
NaIO4
H O
8h
15
80
rt
91
92
97
89
70
95
86
[45]
[46]
[47]
[48]
[49]
[50]
2
H O
2
2
2
2
2
H O
2
H O
2
5
rt
CuBr-urea
MeCN
H O
2
12
80
rt
CuCl S-100
H O
2
O2
O2
24h
3.5 h
20
2
α-Fe O (hυ)
THF
rt
2
3
1
0
Cu/TCOP
H O/EtOH
2
H O
2
70
Present
work
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Scheme 3. Plausible mechanism for hydroxylation of phenylboronic acid.
In order to investigate, the plausible mechanism for hydroxylation of phenyl boronic
acid catalyzed by Cu/TCOP heterogeneous catalyst was proposed in scheme 3. In the first
step the phenyl boronic acid coordinated Cu/TCOP heterogeneous catalyst to obtained
electron deficient boron complex was formed and then followed by insertion of H O in the
2
2
third step to form the borate ionic intermediate and followed by insertion of O-oxygen to the
C-B bond. Finally, then borate intermediates was hydrolysis to obtained expected desired
product. Furthermore, the catalyst Cu/TCOP heterogeneous catalyst was successfully
continued to consecutive cycles.
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4
. Conclusion
In summary, we have demonstrated the facile synthesis of nitrogen-rich triazine
containing covalent organic polymers (Cu/TCOP) has been prepared by the nucleophilic
substitution reaction between melamine and cyanuric chloride then mixture of DMSO and
1,4-dioxane (1:1) at 90 ºC for about 48 h under solvothermal techniques. Further, the
synthesized materials were thoroughly characterized by different techniques. The prepared
Cu/TCOP heterogeneous catalysts exhibited high catalytic activity for promoting to oxidation
reaction variety of aryl boronic acid and H O as oxidant in a EtOH/water (1:1) medium for
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about 25 minutes at ambient temperature to obtain excellent yield (up to 96%) high turnover
number, short reaction time, phosphine-free catalyst, clean reaction and small amount of
catalyst (15 mg), high efficiency under relatively mild reaction conditions and the use of
water as a green solvents and benign, without any other additives, ligands and co catalyst.
Acknowledgments
AS and VS acknowledge the financial support of the Department of Science and
Technology, SERB, Extramural Major Research Project (Grant No. EMR/2015/000969),
Council of Scientific and Industrial Research (CSIR), HRDG, File No. 01(2901)/17/EMR-II,
New Delhi, Department of Science and Technology DST/TM/CERI/C130(G), New Delhi,
India. Further, VS acknowledge to the financial support of the CSIR, New Delhi for
providing SRF file No. 124065/2k17/1, 09/201(0420)/18-EMR-I, New Delhi. We also
acknowledge to UPE, PURSE and DST-FIST for providing instrumental support.
Keywords: Cyanuric chloride. Heterogeneous. Hydroxylation. Melamine. Covalent organic
polymer.
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DOI: 10.1039/C9NJ05759E
Copper Nanoparticles Supported on Highly Nitrogen‐Rich Containing Covalent
Organic Polymers as Heterogeneous Catalyst for ipso-Hydroxylation of Phenylboronic
acid to Phenol
b
Muniyasamy Harikrishnan,a Ganesan Elamathi,a Rajendran
Velu Sadhasivam,
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Balasaravanan, Sepperumal Murugesan and Ayyanar Siva*
aSupramolecular and Organometallic Chemistry Lab, Department of Inorganic Chemistry,
School of Chemistry, Madurai Kamaraj University, Madurai-625 021, Tamil Nadu, India.
bDepartment of chemistry, V. M. K. V Engineering College, Vinayaga Mission's Research
Foundation (Deemed to be university), Salem, Tamil Nadu, India.
E-mail: drasiva@gmail.com (Ayyanar Siva)
Abstract
Here we report to synthesis of highly nitrogen‐rich containing covalent organic
polymers as a solid heterogeneous catalyst Cu/TCOP under solvothermal conditions. The
catalytic activity of the catalyst Cu/TCOP was investigated by focusing on oxidation of
phenylboronic acid under atmospheric conditions in aqueous medium to get very good yield
up to 99% was observed.
HN
HO
OH
HN
B
N
N
N
N
NH
Cu
HN
N
NH
NH
HN
N
NH
NH
Cu
R
Cu(NO3)2
N
N
N
N
N
N
N
N
N
EtOH/H O
2
OH
H2O2
HN
N
N
N
NH
N H .H O
HN
N
N
N
Cu
NH
2
4
2
H
H
N
N
N
Ligand free protocol
Cu/TCOP
Reaction was carried out RT
TCOP good solid supports
HN
N
HN
N
NH
R
Mild oxidation agent, green solvent
Reaction was completed within 10 minutes
TCOP
Cu- Cu NPs