S1

Polysaccharide-based superporous hydrogel embedded with copper

nanoparticles: A green and versatile catalyst for the synthesis of 1,2,3-

triazoles

Jaqueline F. Souza1, Gabriel P. Costa2, Rafael Luque*3, Diego Alves2*

and André R. Fajardo1*

1 Laboratório de Tecnologia e Desenvolvimento de Compósitos e Materiais Poliméricos (LaCoPol),

Universidade Federal de Pelotas (UFPel), Pelotas – RS, Brazil. 2 Laboratório de Síntese Orgânica Limpa

(LASOL), Universidade Federal de Pelotas (UFPel), Pelotas – RS, Brazil 3 Departamento de Quimica

Organica, Universidad de Cordoba, Campus de Rabanales, Cordoba, Spain

e-mail: q62alsor@uco.es, diego.alves@ufpel.edu.br and andre.fajardo@pq.cnpq.br

Contents

1. Thermal analysis...........................................................................................................................S2

2. Visual characterization..........……….......……………………………………………………...S2

3. EDS analyses.................................................................................................................................S3

4. Swelling experiments at different pH and temperature conditions...........................................S3

5. General experimental procedure for the synthesis of 1,4-disubstituted 1,2,3-triazoles...........S4

6. Spectral data of the products........................................................................................................S4

7.Selected Spectra…….....................………...….…………………………....................................S8

Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2018

S2

1. Thermal analysis

Figure S1. TGA (a) and DTG (b) curves recorded for Cs/PVA, Cs/PVA-Cu2+ and

Cs/PVA-CuNP hydrogels.

2. Visual characterization

Figure S2. Photographic images of Cs/PVA (a) and Cs/PVA-CuNP hydrogels at dry

state.

S3

3. EDS analyses

Figure S3. EDS spectrum (a) and EDS mapping analysis (b) recorded from the

Cs/PVA-CuNP surface.

4. Swelling experiments at different pH and temperature conditions

Figure S4. Maximum swelling of Cs/PVA and Cs/PVA-CuNP hydrogels calculated for samples

immersed at different pH (a) and temperature conditions (b) for 24 h.

S4

5. General experimental procedure for the synthesis of 1,4-disubstituted 1,2,3-

triazolesAryl azides 1 (0.157 mmol), terminal alkynes 2 (0.157 mmol), Cs/PVA-CuNP hydrogel (10

mol-%, 1 mg of Cu per hydrogel sample) and a mixture of EtOH/H2O (1:1) (1.5 mL) were added

to a glass vial. Then, the heterogeneous reaction mixture was sonicated for 6 h at room

temperature in an ultrasonic bath. After the total disappearance of starting materials, DCM (3

mL) was added and the reaction mixture was sonicated for additional 5 min. The reaction mixture

was then separated by the Cs/PVA-CuNP using a Pasteur pipette. This procedure was then

repeated for four times and the combined extracts were dried over MgSO4 and concentrated under

vacuum. The crude products obtained were subsequently purified by column chromatography on

silica gel using a mixture of hexane/ethyl acetate as eluent to afford the desired products 3a-h.

All products were characterized by Nuclear Magnetic Resonance (NMR) spectroscopy in a Bruker

Avance DPX 400 spectrometer at 400 MHz (1H) and at 100 MHz (13C). All NMR spectra were

acquired using CDCl3 or DMSO-d6 as deuterated solvents and tetramethylsilane (TMS) was used

as internal standard. The recovered Cs/PVA-CuNP sample was dried under vacuum and could be

reused directly in subsequent reactions. The data of obtained compounds 3a-h are in agreement

with the already published data.1,2

6. Spectral data of the products

1,4-diphenyl-1H-1,2,3-triazole1 (3a). Yield: 0.032 g (92%); white solid; m.p =

NN

N

181-183 °C. 1H NMR (DMSO-d6, 400 MHz) δ = 9.30 (s, 1H), 7.96 (d, J=8.0 Hz, 4H), 7.64 (d,

J=7.8 Hz, 2H), 7.54-7.48 (m, 3H), 7.39 (t, J=7.4 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz) δ =

147.32, 136.65, 130.26, 129.93, 129.00, 128.72, 128.24, 125.35, 120.01, 119.62.

1 Kaboudin, B.; Mostafalu, R.; Yokomatsu, T. Green Chem. 2013, 15, 2266-2274.2 Chen, Z.; Yan, Q.; Liu, Z.; Zhang, Y. Chem. Eur. J. 2014, 20, 17635-17639.

S5

4-(3-nitrophenyl)-1-phenyl-1H-1,2,3-triazole2 (3b). Yield: 0.035 g (84%);

NN

N

NO2

brown yellow solid; m.p = 93-94 °C; 1H NMR (DMSO-d6, 400 MHz) δ = 9.54 (s, 1H), 8.78 (t, J

= 21 Hz, 1H), 8.45 (ddd, J = 8.1, 2.1, 0.8 Hz, 1H), 8.34 (ddd, J = 8.1, 2.1, 0.8 Hz, 1H)., 7.97-7.93

(m, 3H), 7.51 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 7.4 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz) δ =

148.60, 147.72, 137.24, 131.66, 129.92, 129.11, 128.52, 125.93, 125.43, 123.16, 120.06, 114.60.

1-(4-chlorophenyl)-4-phenyl-1H-1,2,3-triazole1 (3c). Yield: 0.026 g (65%);

NN

N

Cl

light yellow solid; m.p = 222-224 °C; 1H NMR (DMSO-d6, 400 MHz) δ = 9.32 (s, 1H), 8.00 (d,

J=8.8 Hz, 2H), 7.94 (d, J=7.8 Hz, 2H), 7.72 (d, J=8.8 Hz, 2H), 7.51 (t, J=7.6 Hz, 2H), 7.39 (t,

J=7.4 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz) δ = 147.53, 135.49, 133.05, 130.13, 130.00,

129.11, 128.43, 125.42, 121.75, 119.77.

4-phenyl-1-(p-tolyl)-1H-1,2,3-triazole1 (3d). Yield: 0.032 g (86%); light

NN

N

yellow solid; m.p = 169-171 °C;1H NMR (CDCl3, 400 MHz) δ = 8.06 (s, 1H), 7.81 (d, J=7.2 Hz,

2H), 7.57 (d, J=8.4 Hz, 2H), 7.35 (t, J=7.5 Hz, 2H), 7.28-7.21 (m, 3H), 2.32 (s, 3H). 13C NMR

(CDCl3, 100 MHz) δ = 148.33, 138.96, 134.85, 130.44, 130.34, 128.98, 128.43, 125.92, 120.49,

117.75, 21.19.

S6

1-(4-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole1 (3e). Yield: 0.034 g

NN

N

MeO

(85%); light yellow solid; m.p = 162-164 °C;1H NMR (CDCl3, 400 MHz) δ = 8.02 (s, 1H), 7.80

(d, J=7.3 Hz, 2H), 7.57 (d, J=8.8 Hz, 2H), 7.34 (t, J=7.5 Hz, 2H), ), 7.25 (t, J=7.3 Hz, 1H), 6.91

(t, J=8.8 Hz, 2H), 3.75 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ = 159.89, 148.26, 130.57, 130.46,

128.97, 128.39, 125.88, 122.20, 117.96, 114.85, 55.70.

1-phenyl-4-(p-tolyl)-1H-1,2,3-triazole1 (3f). Yield: 0.030 g (82%);light

NN

N

yellow solid; m.p = 152-154 °C.1H NMR (CDCl3, 400 MHz) δ = 8.05 (s, 1H), 7.71-7.66 (m, 4H),

7.42 (t, J=7.7 Hz, 2H), 7.33 (t, J=7.4 Hz, 1H), 7.15 (t, J=7.7 Hz, 2H), 2.29 (s, 3H). 13C NMR

(CDCl3, 100 MHz) δ = 148.54, 138.36, 137.16, 129.81, 129.67, 128.74, 127.50, 125.83, 120.52,

117.36, 21.39.

1-phenyl-4-(3-(trifluoromethyl)phenyl)-1H-1,2,3-triazole2 (3g). Yield: NN N

CF3

0.025 g (54%); yellow solid; m.p. = 113-115 °C;. 1H NMR (CDCl3, 400 MHz) δ = 8.19 (s, 1H),

8.05 (s, 1H), 7.98 (d, J=7.3, 1H), 7.67 (d, J=7.7 Hz, 2H), 7.50-7.32 (m, 5H). 13C NMR (CDCl3,

100 MHz) δ = 147.11, 136.90, 131.39 (q, J=32 Hz), 131.18, 129.91, 129.53, 129.07 (d, J=2.8

Hz), 125.02 (q, J=3.7 Hz), 124.11 (q, J=272 Hz), 122.65 (q, J=3.7 Hz), 120.58, 118.32.

S7

4-butyl-1-phenyl-1H-1,2,3-triazole2 (3h). Yield: 0.017 g (55%); White solid;

NN N

m.p = 58-59 °C 1H NMR (CDCl3, 500 MHz) δ = 7.65 (m, 3H), 7.41 (t, J=7.8, 2H), 7.32 (t, J= 7.4 Hz,

1H), 2.71 (t, J=7.7 Hz, 2H), 1.64 (quint., J=7.7 Hz, 2H), 1.34 (sext., J=7.4 Hz, 2H), 0.87 (t, J=7.4 Hz,

3H). 13C NMR (CDCl3, 100 MHz) δ = 149.22, 137.34, 129.72, 128.45, 120.43, 118.88, 31.57, 25.41,

22.38, 13.89.

S8

7. Selected Spectra

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

1.1

3.2

2.2

4.3

1.0

2.50

DM

SO

-d6

7.37

7.39

7.41

7.48

7.50

7.52

7.54

7.62

7.64

7.66

7.95

7.97

9.30

7.37.47.57.67.77.87.98.08.1f1 (ppm)

1.1

3.2

2.2

4.3

7.37

7.39

7.41

7.48

7.50

7.52

7.54

7.62

7.64

7.66

7.95

7.97

Figure 1. 1H NMR (400 MHz) spectrum for compound 3a in DMSO-d6.

NN

N

S9

0102030405060708090100110120130140150160170180190200f1 (ppm)

39.5

2 D

MS

O-d

6

119.

6212

0.01

125.

3512

8.24

128.

7212

9.00

129.

9313

0.26

136.

65

147.

32

120122124126128130f1 (ppm)

119.

6212

0.01

125.

35

128.

2412

8.72

129.

0012

9.93

130.

26

Figure 2. 13C NMR (100 MHz) spectrum for compound 3a in DMSO-d6.

NN

N

S10

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

1.2

2.4

3.4

1.1

1.1

1.1

1.0

2.50

DM

SO

-d6

7.38

7.40

7.42

7.49

7.51

7.53

7.93

7.94

7.94

7.95

7.96

7.97

8.33

8.33

8.33

8.34

8.35

8.35

8.35

8.36

8.44

8.44

8.44

8.44

8.46

8.46

8.46

8.46

8.77

8.78

8.78

9.54

8.748.768.788.80f1 (ppm)

1.1

8.77

8.78

8.78

8.428.448.468.48f1 (ppm)

1.1

8.44

8.44

8.44

8.44

8.46

8.46

8.46

8.46

8.308.328.348.368.38f1 (ppm)

1.1

8.33

8.33

8.33

8.34

8.35

8.35

8.35

8.36

Figure 3. 1H NMR (400 MHz) spectrum for compound 3b in DMSO-d6.

NN

N

NO2

S11

0102030405060708090100110120130140150160170180190200f1 (ppm)

39.5

2 D

MS

O-d

6

114.

6012

0.06

123.

1612

5.43

125.

9312

8.52

129.

1112

9.92

131.

6613

7.24

147.

7214

8.60

Figure 4. 13C NMR (100 MHz) spectrum for compound 3b in DMSO-d6.

NN

N

NO2

S12

-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)

1.2

2.3

2.2

2.2

2.1

1.0

2.50

DM

SO

-d6

7.37

7.39

7.41

7.49

7.51

7.52

7.71

7.73

7.93

7.95

7.99

8.01

9.32

7.357.407.457.507.557.607.657.707.757.807.857.907.958.008.05f1 (ppm)

1.2

2.3

2.2

2.2

2.1

7.37

7.39

7.41

7.49

7.51

7.52

7.71

7.73

7.93

7.95

7.99

8.01

Figure 5. 1H NMR (400 MHz) spectrum for compound 3c in DMSO-d6.

NN

N

Cl

S13

0102030405060708090100110120130140150160170180190f1 (ppm)

39.5

2 D

MS

O-d

6

119.

7712

1.75

125.

4212

8.43

129.

1113

0.00

130.

1313

3.05

135.

49

147.

53

118120122124126128130132134136138140142144146148f1 (ppm)

119.

77

121.

75

125.

42

128.

4312

9.11

130.

0013

0.13

133.

05

135.

49

147.

53

Figure 6. 13C NMR (100 MHz) spectrum for compound 3c in DMSO-d6.

NN

N

Cl

S14

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.9

3.3

2.1

2.2

2.0

1.0

-0.0

0 T

MS

2.32

7.21

7.23

7.24

7.26

7.28

7.33

7.35

7.37

7.55

7.57

7.80

7.82

8.06

7.17.27.37.47.57.67.77.87.9f1 (ppm)

3.3

2.1

2.2

2.0

7.21

7.23

7.24

7.26

7.28

7.33

7.35

7.37

7.55

7.57

7.80

7.82

Figure 7. 1H NMR (400 MHz) spectrum for compound 3d in CDCl3.

NN

N

S15

0102030405060708090100110120130140150160170180190200210f1 (ppm)

21.1

9

77.1

6 C

DC

l3

117.

7512

0.49

125.

9212

8.43

128.

9813

0.34

130.

4413

4.85

138.

96

148.

33

Figure 8. 13C NMR (100 MHz) spectrum for compound 3d in CDCl3.

NN

N

S16

-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)

3.0

2.1

1.1

2.3

2.1

2.0

1.0

-0.0

0 T

MS

3.75

6.90

6.92

7.23

7.25

7.27

7.32

7.34

7.36

7.56

7.58

7.79

7.81

8.02

6.97.07.17.27.37.47.57.67.77.87.9f1 (ppm)

2.1

1.1

2.3

2.1

2.0

6.90

6.92

7.23

7.25

7.27

7.32

7.34

7.36

7.56

7.58

7.79

7.81

Figure 9. 1H NMR (400 MHz) spectrum for compound 3e in CDCl3.

NN

N

MeO

S17

-100102030405060708090100110120130140150160170180190200f1 (ppm)

55.7

0

77.1

6 C

DC

l3

114.

8511

7.96

122.

2012

5.88

128.

3912

8.97

130.

4613

0.57

148.

26

159.

89

Figure 10. 13C NMR (100 MHz) spectrum for compound 3e in CDCl3.

.

NN

N

MeO

S18

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.8

2.1

1.1

2.0

4.1

1.0

0.00

TM

S

2.29

7.14

7.16

7.31

7.33

7.35

7.40

7.42

7.44

7.66

7.68

7.69

7.71

8.05

7.07.17.27.37.47.57.67.77.8f1 (ppm)

2.1

1.1

2.0

4.1

7.14

7.16

7.31

7.33

7.35

7.40

7.42

7.44

7.66

7.68

7.69

7.71

Figure 11. 1H NMR (400 MHz) spectrum for compound 3f in CDCl3.

NN

N

S19

0102030405060708090100110120130140150160170180190200f1 (ppm)

21.3

9

77.1

6 C

DC

l3

117.

3612

0.52

125.

8312

7.50

128.

7412

9.67

129.

8113

7.16

138.

36

148.

54127.0127.5128.0128.5129.0129.5130.0130.5131.0

f1 (ppm)

127.

50

128.

74

129.

6712

9.81

Figure 12. 13C NMR (100 MHz) spectrum for compound 3f in CDCl3.

NN

N

S20

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

5.3

2.0

1.0

1.0

1.0

0.00

TM

S

7.32

7.34

7.36

7.40

7.42

7.44

7.46

7.48

7.50

7.66

7.68

7.97

7.99

8.05

8.19

7.27.37.47.57.67.77.87.98.08.18.28.3f1 (ppm)

5.3

2.0

1.0

1.0

1.0

7.32

7.34

7.36

7.40

7.42

7.44

7.46

7.48

7.50

7.66

7.68

7.97

7.99

8.05

8.19

Figure 13. 1H NMR (400 MHz) spectrum for compound 3g in CDCl3.

NN N

CF3

S21

0102030405060708090100110120130140150160170180190200f1 (ppm)

77.1

6 C

DC

l311

8.32

120.

0512

0.58

122.

5912

2.63

122.

6712

2.71

122.

7512

4.97

125.

0112

5.04

125.

0812

5.46

128.

1712

9.05

129.

0812

9.53

129.

9113

0.91

131.

1813

1.23

131.

5513

1.88

136.

9014

7.11

130.5131.0131.5132.0f1 (ppm)

130.

9113

1.18

131.

2313

1.55

131.

88

120121122123124125126127128f1 (ppm)

120.

0512

0.58

122.

5912

2.63

122.

6712

2.71

122.

75

124.

9712

5.01

125.

0412

5.08

125.

46

128.

17

Figure 14. 13C NMR (100 MHz) spectrum for compound 3g in CDCl3.

NN N

CF3

S22

-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)

3.0

2.1

2.1

2.1

1.0

2.1

3.0

-0.0

0 T

MS

0.85

0.87

0.89

1.30

1.32

1.34

1.35

1.37

1.39

1.60

1.62

1.64

1.66

1.68

2.69

2.71

2.73

7.30

7.32

7.33

7.39

7.41

7.43

7.62

7.65

2.652.702.752.80f1 (ppm)

2.1

2.69

2.71

2.73

1.551.601.651.70f1 (ppm)

2.1

1.60

1.62

1.64

1.66

1.68

1.301.351.40f1 (ppm)

2.1

1.30

1.32

1.34

1.35

1.37

1.39

0.850.90f1 (ppm)

3.0

0.85

0.87

0.89

7.37.47.57.67.7f1 (ppm)

1.0

2.1

3.0

7.30

7.32

7.33

7.39

7.41

7.43

7.62

7.65

Figure 15. 1H NMR (400 MHz) spectrum for compound 3h in CDCl3.

NN N

S23

0102030405060708090100110120130140150160170180190200f1 (ppm)

13.8

9

22.3

825

.41

31.5

7

77.1

6 C

DC

l3

118.

8812

0.43

128.

4512

9.72

137.

34

149.

22

Figure 16. 13C NMR (100 MHz) spectrum for compound 3h in CDCl3.

NN N