1
Copper Nanoparticles Supported on Highly Nitrogen‐Rich Containing Covalent Organic
Polymers as Heterogeneous Catalyst for ipso-Hydroxylation of Phenyl boronic acid to
Phenol
Velu Sadhasivam,b Muniyasamy Harikrishnan,a Ganesan Elamathi,a Rajendran Balasaravanan,a Sepperumal Murugesana and Ayyanar Siva*a
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: [email protected] (Ayyanar Siva)
S. No Content Page No
1 XP spectrum of compound Cu@TCOP for C1s and O1s 2
2 EDS spectrum of compound TCOP and Cu@TCOP 3
3 Elemental analysis of TCOP and Cu@TCOP 4
4 SEM images of TCOP and Cu@TCOP 5
5 1H NMR and 13C NMR spectra of all the phenols derivatives 6
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2020
2
526 528 530 532 534 536 538 540
1500
2250
3000
3750
4500
Co
unts
/s
Binding Energy (eV)
O1s
Figure S1. XP spectra of compound Cu@TCOP for O1s.
282 285 288 291 294
500
1000
1500
2000
2500
Coun
ts/s
Binding Energy (eV)
C1s
Figure S2. XP spectra of compound Cu@TCOP for C1s.
3
Figure S3. EDS spectra of compound TCOP.
Figure S4. EDS spectra of compound Cu@TCOP.
4
Table 1. Elemental atomic weight % of compound TCOP.
Elem: At No Series Unn. C
[Wt %]
Norm. C
[Wt %]
Atom. C
[at. %]
(1 Sigma)
[Wt %]
C-6 K- Series 39.90 39.95 49.74 7.06
N-7 K-Series 25.65 25.68 24.00 5.03
O-8 K-Series 14.86 14.88 15.89 4.19
Si-14 K-Series 12.09 12.11 6.45 0.58
Na-11 K-Series 3.37 3.38 2.20 0.30
Mg-12 K-Series 2.10 2.02 0.84 0.08
Ca-20 K-Series 2.03 2.00 0.88 0.05
Total 100.00 100.00 100.00
Table 2. Elemental atomic weight % of compound Cu/TCOP.
Elem: At No Series Unn. C
[Wt %]
Norm. C
[Wt %]
Atom. C
[at. %]
(1 Sigma)
[Wt %]
C-6 K- Series 44.10 43.84 52.76 8.54
N-7 K-Series 31.15 29.98 25.17 5.92
O-8 K-Series 21.51 20.71 19.11 5.39
Cu -29 K-series 3.34 3.29 0.71 0.12
Total 100.00 100.00 100.00
Spectrum: sample 1357
El AN Series unn. C norm. C Atom. C Error (1 Sigma) [wt.%] [wt.%] [at.%] [wt.%]-----------------------------------------------------C 6 K-series 54.10 43.74 52.76 8.54O 8 K-series 31.65 25.58 23.17 5.92N 7 K-series 21.66 17.51 18.11 5.39Si 14 K-series 8.17 6.60 3.41 0.40Na 11 K-series 2.35 1.90 1.20 0.23Cu 29 K-series 3.31 2.68 0.61 0.14Ca 20 K-series 1.68 1.36 0.49 0.09Cl 17 K-series 0.78 0.63 0.26 0.06----------------------------------------------------- Total: 123.70 100.00 100.00
5
Figure S5. SEM images of compound (a) TCOP (b) Cu/TCOP.
6
1H NMR characterization data for all the biphenyl coupled products.
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
2.01
1.99
0.99
1.00
6.75
6.77
7.27
7.29
9.61
10.9
4
Figure S6: 1H NMR spectrum of compound 4-hydroxy benzaldehyde.
0102030405060708090100110120130140150160170180190200f1 (ppm)
77.3
277
.64
77.9
6
117.
2711
9.71
120.
57
133.
6913
6.75
161.
29
196.
66
Figure S7: 13C NMR spectrum of compound 4-hydroxy benzaldehyde.
OH
CHO
OH
CHO
7
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
1.00
1.01
1.02
1.01
1.00
6.57
6.90
6.92
6.94
7.12
7.14
7.20
7.21
7.37
7.39
Figure S8: 1H NMR spectrum of compound 2-chloro phenol.
0102030405060708090100110120130140150160170180190200f1 (ppm)
77.0
877
.40
77.7
2
116.
6712
0.24
121.
63
128.
4712
9.43
151.
46
Figure S9: 13C NMR spectrum of compound 4-chloro phenol.
OHCl
OHCl
8
Figure S10: 1H NMR spectrum of compound phenol.
0102030405060708090100110120130140150160170180190
f1 (ppm)
76.9
077
.22
77.5
4
115.
57
121.
16
129.
91
155.
19
Figure S11: 13C NMR spectrum of compound phenol.
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
0.46
0.99
0.50
1.00
5.87
6.82
6.84
6.90
6.92
6.94
7.20
7.21
7.23
OH
OH
9
0123456789101112131415f1 (ppm)
0.99
1.00
1.01
1.02
1.00
1.00
1.07
1.01
-0.0
0
7.14
7.16
7.26
7.43
7.44
7.46
7.61
7.63
7.65
7.80
7.82
7.98
8.00
8.35
8.37
10.8
3
13.1
7
Figure S12: 1H NMR spectrum of compound 2-Napthol.
0102030405060708090100110120130140150160170180190200f1 (ppm)
76.8
777
.19
77.5
0
111.
23
118.
5811
9.12
124.
5012
7.74
129.
0912
9.46
132.
82
139.
08
164.
86
193.
21
Figure S13: 13C NMR spectrum of compound 2-Napthol.
OH
OHC
OH
OHC
10
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5f1 (ppm)
1.05
3.00
4.03
3.39
4.51
7.26
7.28
Figure S14: 13C NMR spectrum of compound 4-Methoxy Phenol.
0102030405060708090100110120130140150160170f1 (ppm)
64.9
1
76.9
577
.27
77.5
9
127.
1012
7.57
128.
54
140.
93
Figure S15: 13C NMR spectrum of compound 4-Methoxy Phenol.
11
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.07
1.00
2.02
2.00
2.23
6.25
6.71
6.73
6.97
6.98
Figure S16: 1H NMR spectrum of compound 4-Methyl Phenol.
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
20.5
6
76.9
177
.23
77.5
5
115.
39
130.
28
152.
97
Figure S17: 13C NMR spectrum of compound 4-Methyl Phenol.
12
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
0.99
2.05
2.00
5.84
6.72
6.74
7.11
7.13
Figure S18: 1H NMR spectrum of compound 4-Chlorophenol.
0102030405060708090100110120130140150160170180190200f1 (ppm)
76.9
276
.96
77.2
477
.28
77.5
9
116.
8611
6.88
125.
9612
6.00
129.
75
153.
69
Figure S19: 13C NMR spectrum of compound 4-ChloroPhenol.
13
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
1.19
2.06
2.00
2.49
3.40
6.13
6.58
6.60
7.36
7.38
Figure S20: 1H NMR spectrum of compound 4-hydroxyl benzonitrile.
0102030405060708090100110120130140150160170180190200f1 (ppm)
39.7
940
.06
40.3
440
.61
40.9
0
96.3
8
114.
30
121.
53
134.
29
153.
84
. Figure S21: 13 C NMR spectrum of compound 4-hydroxyl benzonitrile.
14
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
1.06
2.01
2.00
6.04
6.55
6.58
7.65
7.68
Figure S22: 1H NMR spectrum of compound 4-hydroxylacetophenone.
-100102030405060708090100110120130140150160170180190200210220230240250f1 (ppm)
26.6
9
39.7
740
.05
40.3
340
.61
40.8
7
113.
32
125.
71
131.
43
154.
45
195.
83
Figure S23: 1H NMR spectrum of compound 4-hydroxylacetophenone.
15
1H and 13C NMR data for all the derivatives
Phenol 1a Compound 1a was prepared according to the general
procedure to give a colourless viscous liquid with 99% yield. 1H
NMR (400 MHz, CDCl3) δ 7.21 (t, J = 7.0 Hz, 2H), 6.92 (t, J =
6.8 Hz, 1H), 6.83 (d, J = 7.5 Hz, 2H), 5.87 (s, 1H). 13C NMR
(101 MHz, CDCl3) δ 155.19 (s), 129.91 (s), 121.16 (s), 115.57
(s), 77.54 (s), 77.22 (s), 76.90 (s).
4-hydroxyl benzaldehyde (1b) Compound 1b was prepared
according to the general procedure to give a colourless solid with
92% yield. 1H NMR (400 MHz, CDCl3) δ 10.94 (s, 1H), 9.61 (s,
1H), 7.28 (d, J = 7.4 Hz, 2H), 6.76 (d, J = 7.5 Hz, 2H). 13C NMR
(101 MHz, CDCl3) δ 196.66 (s), 161.29 (s), 136.75 (s), 133.69
(s), 120.57 (s), 119.71 (s), 117.27 (s), 77.96 (s), 77.64 (s), 77.32
(s).
4-chlorophenol (1c) Compound 1c was prepared according to
the general procedure to give a light brown solid with 95% yield.
1H NMR (400 MHz, CDCl3) δ 7.12 (d, J = 7.4 Hz, 2H), 6.73 (d,
J = 7.5 Hz, 2H), 5.84 (s, 1H). 13C NMR (101 MHz, CDCl3) δ
153.69 (s), 129.75 (s), 125.98 (d, J = 4.0 Hz), 116.87 (d, J = 2.5
Hz), 77.59 (s), 77.26 (d, J = 4.0 Hz), 76.94 (d, J = 3.9 Hz).
6-hydroxy-2-naphthaldehyde (1d) Compound 1d was
prepared according to the general procedure to give a colourless
solid with 80% yield. 1H NMR (400 MHz, CDCl3) δ 13.17 (s,
1H), 10.83 (s, 1H), 8.36 (d, J = 8.3 Hz, 1H), 7.99 (d, J = 8.9 Hz,
1H), 7.81 (d, J = 7.7 Hz, 1H), 7.63 (t, J = 7.5 Hz, 1H), 7.44 (t, J
= 7.2 Hz, 1H), 7.15 (d, J = 8.9 Hz, 1H). 13C NMR (101 MHz,
CDCl3) δ 193.21 (s), 164.86 (s), 139.08 (s), 132.82 (s), 129.46
(s), 129.09 (s), 127.74 (s), 124.50 (s), 119.12 (s), 118.58 (s),
111.23 (s), 77.50 (s), 77.19 (s), 76.87 (s).
OH
OH
OHC
OH
Cl
OH
OHC
16
4-methoxyphenol (1e) Compound 1e was prepared according to
the general procedure to give a colourless solid with 85%
yield13C NMR (101 MHz, CDCl3) δ 140.93 (s), 128.54 (s),
127.57 (s), 127.10 (s), 77.59 (s), 77.27 (s), 76.95 (s), 64.91 (s).
p-cresol (1f) Compound 1f was prepared according to the
general procedure to give a colourless viscous liquid with 87%
yield. 1H NMR (400 MHz, CDCl3) δ 6.98 (d, J = 7.2 Hz, 2H),
6.72 (d, J = 6.8 Hz, 2H), 6.25 (s, 1H), 2.23 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 152.97 (s), 130.28 (s), 115.39 (s), 20.56 (s).
2-chlorophenol (1g) Compound 1g was prepared according to
the general procedure to give a colourless solid with 80% yield.
1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.4 Hz, 1H), 7.21 (d,
J = 7.0 Hz, 1H), 7.13 (d, J = 7.4 Hz, 1H), 6.92 (t, J = 6.9 Hz,
1H), 6.57 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 151.46 (s),
129.43 (s), 128.47 (s), 121.63 (s), 120.24 (s), 116.67 (s), 77.72
(s), 77.40 (s), 77.08 (s).
4-hydroxybenzonitrile (1h) Compound 1h was prepared
according to the general procedure to give a light brown colour
solid with 78% yield. 1H NMR (300 MHz, DMSO) δ 7.37 (d, J
= 7.0 Hz, 2H), 6.59 (d, J = 7.0 Hz, 2H), 6.13 (s, 1H). 13C NMR
(75 MHz, DMSO) δ 153.84 (s), 134.29 (s), 121.53 (s), 114.30
(s), 96.38 (s), 44.93 – 42.02 (m), 41.18 (s), 40.76 (d, J = 21.4
Hz), 40.20 (d, J = 20.9 Hz), 39.79 (s).
1-(4-hydroxyphenyl)ethan-1-one (1i) Compound 1i was
prepared according to the general procedure to give a light
yellow solid with 72% yield. 1H NMR (300 MHz, DMSO) δ 7.66
(d, J = 8.5 Hz, 2H), 6.56 (d, J = 8.6 Hz, 2H), 6.04 (s, 1H). 13C
NMR (75 MHz, DMSO) δ 195.83 (s), 154.45 (s), 131.43 (s),
OH
MeO
OH
HOCl
NC
OH
H3COC
OH
17
125.71 (s), 113.32 (s), 40.87 (s), 40.47 (d, J = 20.8 Hz), 39.91
(d, J = 21.4 Hz), 39.71 – 39.53 (m), 26.69 (s).
2-Nitro phenol 1j Compound 1j was prepared according to the
general procedure to give a light yellow solid with 54% yield. 1H
NMR (400 MHz, CDCl3) δ 10.59 (s, 1H), 8.11 (d, J = 8.3 Hz,
1H), 7.59 (dd, J = 10.8, 4.2 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H),
7.00 (t, J = 7.5 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 155.13
(s), 137.57 (s), 133.69 (s), 125.07 (s), 120.24 (s), 119.97 (s),
77.39 (s), 77.07 (s), 76.75 (s).
OH
NO2
