Post on 05-Apr-2020
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New Journal of Chemistry
Nitrogen enriched polytriazine as metal-free heterogeneous catalyst for the
Knoevenagel reaction under mild conditions
Monika Chaudhary and Paritosh Mohanty*
Functional Materials Laboratory, Department of Chemistry, IIT Roorkee, Uttarakhand-
247667, India
E-mail: pmfcy@iitr.ac.in, paritosh75@gmail.com
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 2018
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N N
N
N N
N NH2
NH2
H2N Cl
Cl
Cl
N
N
N
N N
N
N
N
N
HN NH
HN
HN HN
HNHN
N N
N
N N
NNHNH NHHN
N
N
N
NH
+Melamine Cyanuric Chloride
140 0C, 400W, 30 min
Scheme S1. Reaction scheme for the synthesis of metal-free nitrogen-enriched nanoporous
polytriazine (NENP-1) organocatalyst.
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Figure S1. TEM image of NENP-1 (inset: SAED pattern of NENP-1).
10 20 30 40 50 60 70
Inte
nsity
(a.u
)
Differaction angle (2)Figure S2. XRD pattern of NENP-1.
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200 400 600 800
0
20
40
60
80
100
Temperature (°C)
Wei
ght (
%)
0
200
400
600
800
DTG
(g/
min
)
Figure S3. TGA/DTG of NENP-1 in air at a heating rate of 5 °C min-1.
5
4000 3500 3000 2500 2000 1500 1000 500
(c)
(b)
Wavenumber (cm-1)
Tran
smitt
ance
(a.u
)
(a)
Figure S4. FT-IR spectra of (a) Benzylidinemalononitrile, (b) Benzaldehyde, and (c)
Malononitrile.
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200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+
O CN
CN
Chemical Shift (ppm)
(a)
12 10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+
O CN
CN
(b)
Chemical Shift (ppm)
Figure S5. (a) 13C and (b) 1H NMR spectra of benzylidinemalononitrile.
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Figure S6. (a) GC and (b) MS spectrum of benzylidinemalononitrile.
(b)
(a)
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CHO
CN
H2C
CN
Solvent
Catalyst 25 °C
NC
CN
Scheme S2. Synthesis of benzylidinemalononitrile from benzaldehyde and malononitrile.
Table S1. Catalytic data of the NENP-1 catalysed model Knoevenagel reaction at various
reaction conditions.
Solvent Volume (mL/mL)
Time (min)
Catalyst amount (wt%)
Yield (%)
THF 1.0/0 30 4.5 37THF/H2O 0.5/0.5 30 4.5 95Methanol 1.0/0 30 4.5 85
Methanol/H2O 0.5/0.5 30 4.5 94Ethanol 1.0/0 30 4.5 87
Ethanol/H2O 0.5/0.5 30 4.5 93H2O 1.0/0 30 4.5 48
Dioxane 1.0/0 30 4.5 41Dioxane/H2O 0.5/0.5 30 4.5 98Dioxane/H2O 0.5/0.5 30 1.9 35Dioxane/H2O 0.5/0.5 90 1.9 46Dioxane/H2O 0.5/0.5 30 8.6 98Dioxane/H2O 0.5/0.5 10 8.6 75Dioxane/H2O 0.5/0.5 02 4.5 45Dioxane/H2O 0.5/0.5 05 4.5 60Dioxane/H2O 0.5/0.5 10 4.5 71
General conditions: Benzaldehyde (1.0 mmol), Malononitrile (1.0 mmol) at 25 °C.
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0 4 8 12 16
20
40
60
80
100
Yiel
d (%
)
Catalyst loading (wt%)
Figure S7. Effect of catalyst loading on yield (%) of benzyldinemalononitrile.
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200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+O
MeO
CN
CNMeO
Chemical Shift (ppm)
(a)
10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+O
MeO
CN
CNMeO
Chemical Shift (ppm)
(b)
Figure S8. (a) 13C and (b) 1H spectra NMR spectra of 4-methoxy benzylidinemalononitrile.
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Figure S9. (a) GC and (b) MS spectrum of 4-methoxy benzylidinemalononitrile.
(a)
(b)
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200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+
O CN
CNBrBr
Chemical Shift (ppm)
(a)
10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+
O CN
CNBrBr
Chemical Shift (ppm)
(b)
Figure S10. (a) 13C and (b) 1H NMR spectra of 2-bromobenzylidinemalononitrile.
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Figure S11. (a) GC and (b) MS spectrum of 2-bromobenzylidinemalononitrile.
(a)
(b)
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200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+
O
Br
CN
CNBr
Chemical Shift (ppm)
(a)
10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+
O
Br
CN
CNBr
Chemical Shift (ppm)
(b)
Figure S12. (a) 13C and (b) 1H NMR spectra of 4-bromobenzylidinemalononitrile.
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Figure S13. (a) GC (b) MS spectrum of 4-bromobenzylidinemalononitrile.
(a)
(b)
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Figure S14. (a) GC and (b) MS spectrum of 2-nitrobenzylidinemalononitrile.
(a)
(b)
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10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+
O
NO2
CN
CNNO2
Chemical Shift (ppm)
(a)
200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+
O
NO2
CN
CNNO2
Chemical Shift (ppm)
(b)
Figure S15. (a) 1H and (b) 13C NMR spectra of 2-nitrobenzylidinemalononitrile.
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Figure S16. (a) GC and (b) MS spectrum of 4-nitrobenzylidinemalononitrile.
(a)
(b)
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10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)+
O
O2N
CN
CNO2N
Chemical Shift (ppm)
(a)
200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)+
O
O2N
CN
CNO2N
Chemical Shift (ppm)
(b)
Figure S17. (a) 1H and (b) 13C NMR spectra of 4-nitrobenzylidinemalononitrile.
20
10 8 6 4 2 0
CN
CN NENP-1Solvent
RT (30 min)
+OCN
CN
Chemical Shift (ppm)
(a)
200 180 160 140 120 100 80 60 40 20 0
CN
CN NENP-1Solvent
RT (30 min)
+OCN
CN
Chemical Shift (ppm)
(b)
Figure S18. (a) 1H and (b) 13C NMR spectra of α-Napthaldehyde.
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Figure S19. (a) GC and (b) MS spectrum of α-Napthaldehyde.
(a)
(b)
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Table S2. Comparison of experimental conditions for the synthesis of metal-free
heterogeneous organocatalysts and their catalytic performance in Knoevenagel reaction.
Organocatalysts Synthesis conditions Catalysis ReferencesSynthesismethod
Temperature(°C)
Time(h)
Temperature (°C)
Time (min)
Yield (%)
MFCMP-1 Oxidative coupling
polymerization
60 72 25 240 99 S1
JUC-Z12 Oxidative cyclo-dehydrogenation
130 72 25 1440 97 S2
BF-COF-1 Schiff base condensation
120 120 25 600 96 S3
MPU Solvothermal synthesis
150 72 50 840 98 S4
MCN Carbonization 550 3 120 12 95 S5
g-C3N4 Thermal condensation
550 8 40 120 98 S6
PANF Thermal condensation
145 6 70 90 97 S7
NENP-1 Microwave-assisted
condensation
140 0.5 25 30 98 Current work
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References
S1. Y. Zhang, S. A, Y. Zou, X. Luo, Z. Li, H. Xia, X. Liu and Y. Mua, J. Mater. Chem. A, 2014, 2,
13422-13430.
S2. B. Liu, T. Ben, J. Xu, F. Deng and S. Qiu, New J. Chem., 2014, 38, 2292-2299.
S3. Q. Fang, S. Gu, J. Zheng, Z. Zhuang, S. Qiu, and Y. Yan, Angew. Chem. Int. Ed., 2014, 53, 2878 -
2882.
S4. S. K. Dey, N. D. S. Amadeu and C. Janiak, Chem. Commun., 2016, 52, 7834-7837.
S5. M. B. Ansari, H. Jin, M. N. Parvin and S. Park, Catal. Today, 2012, 185, 211-216.
S6. L. Zhang, H. Wang, W. Shen, Z. Qin, J. Wang and W. Fan, J. Catal., 2016, 344, 293-302.
S7. G. Li, J. Xiao and W. Zhang, Green Chem., 2011, 13, 1828-1836.