Co-catalyst and solvent free nitrogen rich triazole based organocatalysts for cycloaddition of CO2 into epoxide

Article abstract of DOI:10.1016/j.mcat.2020.111071

A general synthesis of triazole-based catalysts remains a significant challenge. Consequently, triazole-based catalysts are rarely studied. Herein, the first report is presented for the construction of cyclic carbonates using triazole-based organocatalyst

Full text of DOI:10.1016/j.mcat.2020.111071

Molecular Catalysis 493 (2020) 111071
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Co-catalyst and solvent free nitrogen rich triazole based organocatalysts for
cycloaddition of CO into epoxide
2
Suleman Sulemana,b, Hussein A. Younusa,e,f,*, Zafar A.K. Khattak , Habib Ullah , Mirella Elkadi ,
a
a
g
a,b,c,d,
Francis Verpoort
a
*
Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University
of Technology, Wuhan, 430070, PR China
b
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, PR China
c
Ghent University - Global Campus Songdo, 119 Songdomunhwa-Ro, Yeonsu-Gu, Incheon, 406-840, South Korea
d
National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk, 634050, Russian Federation
College of Materials Science and Engineering, Hunan University, Changsha, 410082, PR China
Chemistry Department, Faculty of Science, Fayoum University, Fayoum, 63514, Egypt
Chemistry Department, College of Science, Khalifa University, Abu Dhabi, UAE
e
f
g
A R T I C L E I N F O
A B S T R A C T
Keywords:
A general synthesis of triazole-based catalysts remains a significant challenge. Consequently, triazole-based
catalysts are rarely studied. Herein, the first report is presented for the construction of cyclic carbonates using
triazole-based organocatalysts, which is a crucial technology to a genuinely sustainable and atom-efficient
economy. A series of triazole-based organocatalysts was synthesized, entirely characterized by FTIR, NMR, mass
spectrometry, and elemental analysis. This work is mainly based on the construction of nucleophilic-electrophilic
bifunctional catalysts (N-rich triazole ring-carboxylic group) combined with substituents, which evaluate the
Carbon dioxide
Organocatalysts
Homogeneous catalysis
Cyclo addition
Cyclic carbonates
2
vital effect of substituents for the catalytic cycloaddition reaction of CO into epoxide. In general, various sys-
tems required the Lewis basic site in the form of cocatalyst or solvent to be optimally effective. However, our
designed catalyst contained Lewis basic and acidic sites. It, therefore, can catalyze the reaction proficiently
without the aid of solvent, cocatalysts and can perform at ambient pressure of CO (1 bar) to produce different
2
cyclic carbonates. Moreover, the catalyst is reusable, maintaining the same activity along with remarkable
catalyst stability.
1. Introduction
production of glycols [8,9]. Indeed on the significant application of
cyclic carbonates, this reaction has been extensively investigated using
Utilization of CO
2
being abundant, inexpensive, C1 carbon, and a
a long series of catalysts, including both homogeneous and hetero-
geneous catalysts.
renewable source has great importance for the synthesis of cyclic car-
bonates. The ultimate aim of CO fixation is, to reduce the emission of
carbon dioxide in the atmosphere, generated from fossil fuels.
Therefore, the title reaction plays an important role in decreasing the
rising level of greenhouse gases, especially CO
be synthesized on a low scale; however, it is an attractive means of
chemically fixing CO due to the widespread utility of cyclic carbo-
nates. Such as polar aprotic solvents, cosmetics, intermediates for the
preparation of pharmaceuticals and fine chemicals, as electrolytes in
lithium-ion batteries, and as raw materials for polymers. [1–7] Cyclic
carbonates are also applied as intermediate in Asahi-Kasei synthesis of
polycarbonates and as intermediates in Shell’s Omega process for the
2
These catalytic systems include ionic liquids [10–13], metal com-
plexes [14–22], metal oxide [23], alkali metal halides and carbonates
[24–26], phosphonium salts/quaternary ammonium [27,28], func-
tional polymer [29,30], mesoporous materials [31,32], MOFs [33–35],
COFs [25,36] and core-shell of organic-inorganic hybrid microspheres
[37]. Including metal-based catalysts, transition metal-based catalysts
coupled with a quaternary ammonium salt as a cocatalyst exhibited
excellent catalytic activity for the synthesis of cyclic carbonate at mild
conditions [38–40]. However, the metal-based synthetic procedure is
complex, costly, consists of multi-steps, and needs high pressure and
hence limits its application on an industrial scale. In recent years,
2
. As cyclic carbonate can
2
⁎
Corresponding authors at: Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis
and Processing, Wuhan University of Technology, Wuhan, 430070, PR China.
E-mail addresses: hay00@fayoum.edu.eg (H.A. Younus), francis.verpoort@ghent.ac.kr (F. Verpoort).
https://doi.org/10.1016/j.mcat.2020.111071
Received 7 April 2020; Received in revised form 19 May 2020; Accepted 6 June 2020
2468-8231/ © 2020 Elsevier B.V. All rights reserved.

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
metal-free catalysts have attracted more attention for the synthesis of
cyclic carbonates, because of the remarkable feature of organocatalysts
such as less toxic, more sustainable, easy accessibility, cost-effective
and more important easily to handle [41,42]. So far, several metal-free
catalysts have been developed for the title reaction by various re-
searchers. Metal-free catalytic systems including ammonium salts [43],
phosphonium salts [44,45], and imidazolium salts [46,47] have been
reported to generate cyclic carbonates. In addition, two-component
systems containing quaternary ammonium salts and a polyol have also
been studied. However, halides, as part of the system, may limit the use
of these catalysts due to their corrosive nature towards the steel re-
actors [48]. Shen et al. reported 4-dimethyl aminopyridine (DMAP)
2. Experimental section
2.1. Synthesis and characterization of catalysts
The compounds A–D were synthesized by the reported system, [55]
with some modifications. In a typical procedure, sodium ascorbate
(0.32 mmol) and CuSO
4 2
·5H O (0.16 mmol) were dissolved in 1.0 mL
H
2
O poured into a two-necked flask equipped with Ar atmosphere (the
click catalyst). Then, a series of compounds such as 2-azido-1,3,5-tri-
methyl benzene, azidobenzene, fluorobenzene, nitrobenzene
(3.26 mmol, 1.0 equiv.) and propiolic acid (3.92 mmol, 1.2 equiv.) were
carefully added in 0.5 mL ter-BuOH and injected to the already pre-
pared click catalyst solution. Under inert atmosphere and at room
temperature, the reaction mixture was stirred for 24 h. After that, 15 mL
2
conjunction with salen ligands for the chemical fixation of CO and
º
epoxide into cyclic carbonates at 120 C and 35 bar. [49] Additionally,
Hydrogen-Bond-Donation (HBD) catalysis has attracted much attention
as a greener alternative along with good to excellent yields of cyclic
saturated NaHCO
desired precipitate was washed twice with ether and filtered. Subse-
quently 100 mL H SO solution was added to the desired product, fol-
lowed by extraction with ethyl acetate. The anhydrous Na SO was
3
solution was added to quench the reaction, and the
carbonate from CO
2
and epoxide under mild conditions. Several ex-
2
4
amples of HBD organocatalysts have been reported such as 2-pyr-
idinemethanol/(n-tetrabutylammonium iodide) TBAI, [50] graphene
oxides/dimethylformamide (DMF) [51], ascorbic acid/TBAI [52],
squaramide/TBAI, [53] etc. More recently, North and co-workers de-
2
4
used for drying the organic fractions and then filtered. The obtained
filtrate was evaporated and dried under vacuum at 30−40 °C.
2
veloped salophen organocatalytic systems for the insertion of CO into
epoxides at high temperature, 120 °C, along with solvent (2-Me THF)
under 30 bar pressure. [54] However, still, the use of solvents, ad-
ditives, high pressure, and high temperature are required. One im-
portant point related to the sustainability of the process is the high-
temperature value, which is a great problem in the balance of utiliza-
2.2. Compound (A) Yield: 73 %
1
H-NMR (500 MHz, CDCl ) δ 6.84 (s, 2 H), 2.33 (s, 6 H), 2.26 (s,
3
3 H); 13C-NMR (126 MHz, CDCl3) δ 135.3, 134.3, 131.8, 129.5, 20.7,
18.0.
tion/emission of CO
effective catalytic protocol such as metal-free, cocatalyst free, and
mainly working at low temperature and ambient pressure of CO . Here,
keeping these concerns in mind, we designed nitrogen-rich triazole
based organocatalysts, the green candidate for the generation of cyclic
carbonates. This work is based on a detailed study of N-rich triazole
organocatalysts and its substituents effect, which points out the im-
2
. Therefore, there is a high demand to develop an
Elemental Analysis: Calcd for C12
18.17; O, 13.84. Found: C, 62.73; H, 6.07; N, 18.57; FTIR (neat):
νmax = 3149, 3110, 2958, 2920, 2647, 2569, 1689, 1538, 1503, 1409,
13 3 2
H N O : C, 62.33; H, 5.67; N,
2
−
1
1355, 1245, 1191, 1035, 930, 852, 770, 584, 544 cm ; The HR-ESI
-MS (positive) of catalyst A exposed to molecular ion peak at m/
+
+
z = 210.100 correspond to [C12
logue to [C12 ].
13 3 2
H N O +Na ] , [56] almost ana-
13 3 2
H N O
portant role of substituents for cycloaddition reaction of CO
oxide catalysis. The specially designed organocatalytic system, bearing
CO activation sites, brönsted acidic center, and nucleophilic center,
Fig.1) helps to construct cyclic carbonate under solvent-free, cocata-
lyst-free and at low-pressure i-e., 1 bar. The catalyst synthesis is facile,
cost-effective, and more delightfully reusable and stable. Till now, from
the best of our knowledge, we report for the first time the triazole or-
ganocatalysts, which displays interesting results for the title reaction.
These organocatalysts will open a new gateway for non-redox catalytic
2
into ep-
2
2.3. Compound (B) Yield
(
71 %: 1H NMR (500 MHz, Chloroform-d) δ 8.64 (s, 1 H), 7.80 (d, J
13
=7.8 Hz, 2 H), 7.60 (d, J =8.1 Hz, 2 H), 7.55 (t, J =7.4 Hz, 1 H);
NMR (126 MHz, CDCl ) δ 163.53, 139.89, 136.25, 130.06, 126.25,
120.92, 76.77. Elemental Analysis: Calcd for C : C, 57.14; H,
C
3
9 7 3 2
H N O
3.73; N, 22.21; O, 16.91. Found: C, 57.54; H, 4.13; N, 22.61; FTIR
(neat): νmax = 3479, 3136, 2894, 2806, 2727, 2634, 2557, 1988, 1809,
2
CO fixation in cyclic carbonates.
1
9
697, 1652, 1596, 1552, 1504, 1404, 1321, 1251, 1168, 1041, 991,
18, 850, 761, 683, 567, 507, 428 cm ; The HR-ESI-MS (positive):
: 189.17; Found = 190.061.
−1
9 7 3 2
m/z calcd. for C H N O
Fig. 1. Triazole organocatalysts design along with active sites.
2

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
Scheme 1. General procedure for the synthesis of catalysts (A-D).
Fig. 2. Catalytic activities for triazole-based organocatalysts. Reaction conditions: Epichlorohydrin 10 mmol, Catalyst 0.02 mmol, Pressure 1 bar, Temperature
20 °C, time 12 h.
1
2.4. Compound (C) Yield: 68 %
9 6 3 2
Calcd for C H FN O : C, 52.18; H, 2.92; F, 9.17; N, 20.28; O, 15.45
Found: C, 52.58; H, 3.32; N, 20.68; FTIR (neat): νmax = 3427, 3176,
3091, 2958, 2920, 2850, 2758, 2694, 2653, 2580, 1716, 1697, 1600,
1560, 1544, 1508, 1473, 1419, 1350, 1288, 1267, 1247, 1218, 1174,
1110, 1035, 987, 925, 846, 817, 759, 669, 628, 570, 545, 514, 468;
1H NMR (500 MHz, DMSO-d
) δ 9.16 (d, J = 1.6 Hz, 1 H), 7.90 –
6
7
=
1
.85 (m, 1 H), 7.69 – 7.63 (m, 1 H), 7.63 – 7.56 (m, 1 H), 7.47 (t, J
1
3
7.6 Hz, 1 H); C NMR (126 MHz, DMSO) δ 161.83, 155.64, 140.70,
32.43, 130.82, 126.94, 117.52, 39.83, 39.49. Elemental Analysis:
9 6 3 2
The HR-ESI-MS (positive): m/z calcd. for C H FN O : 207.16; Found
3

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
Scheme 2. Proposed catalytic mechanism for cyclic carbonate synthesis catalyzed by A.
[
C
9
H
6
FN
3
O
2
+Na+]+: 230.033.
the target reaction at ambient pressure without any solvents and co-
catalysts. A simple and straightforward, well-designed series of triazole
ring containing compounds bearing maximum basicity and competence
2
.5. Compound (D) Yield
2
to adsorb CO were designed, demonstrating an incredible feature for
5 %: 1H NMR (500 MHz, DMSO-d6) δ 9.62 (s, 1 H), 8.82 (s, 1 H),
13
using a substituted triazole ring as a bidentate ligand. Triazole based
organocatalysts (A–D in Scheme 1) were achieved in good yields and
synthesized according to a reported method. [57,58] A series of bi-
dentate ligands such as 1-mesityl-1H-1,2,3-triazole-4-carboxylic acid, 1-
phenyl-1H-1,2,3-triazole-4-carboxylic acid, 1-(3-fluorophenyl)-1H-
7
8
1
1
2
.47 (s, 1 H), 8.35 (s, 1 H), 7.94 (s, 1 H); C NMR (126 MHz, DMSO) δ
61.78, 148.96, 141.43, 137.28, 132.00, 128.21, 127.10, 124.11,
15.90, 40.16. Elemental Analysis: Calcd for C
9 6 4 4
H N O : C, 46.16; H,
.58; N, 23.93; O, 27.33. Found: C, 46.56; H, 2.98; N, 24.33; FTIR
neat): νmax = 3572, 3151, 3097, 2873, 2777, 2586, 2534, 2362, 1701,
1,2,3-triazole-4-carboxylic acid and 1-(3-nitrophenyl)-1H-1,2,3-tria-
(
zole-4-carboxylic acid was synthesized by copper-catalyzed azide-al-
kyne click cycloaddition reaction of propiolic acid and aryl azides
(Scheme 1 A). The structures of these organocatalysts were established
based on NMR (S1-S4), HR-ESI-MS (S5-S6), elemental analysis, and
FTIR (S7-S8). The HR-ESI-MS of catalysts A, C, and D revealed mole-
cular ion peaks at m/z = 210.10, 207.16, and 234.17 corresponding to
1
535, 1438, 1406, 1350, 1294, 1253, 1184, 1089, 1043, 979, 898, 873,
−
1
808, 779, 740, 669, 574, 528, 453 cm ; HR- ESI-MS (positive): m/z
+
+
calcd. for C
9
H
6
N
4
O
4
: 234.17; Found [C
fixation into epoxides
The catalyst (4.62 mg, 0.02 mmol) along with 2 mmol of epoxides
9 6 4 4
H N O +Na ] : 257.028.
2.6. General procedure for CO
2
[
Catalysts A, B, C + Na], respectively. The structure of these organo-
catalysts demonstrates two significant functions, Lewis acidic and
Brønsted acidic sites, for the efficient chemical fixation of CO to ep-
were added in a 30 mL stainless-steel autoclave equipped with a mag-
netic stirring bar. The reaction mixture in the autoclave was purged
with carbon dioxide gas at room temperature. After that, the reactor
was dipped in the preheated oil bath, and then pressurized to low at-
mospheric pressure i-e 1 bar of CO . After a particular time, the reaction
2
was stopped, cooled the reactor slowly to room temperature. An aliquot
2
oxides. These two important functions encouraged us to investigate the
utility of the newly developed catalysts for the generation of cyclic
carbonate at ambient pressure of CO .
2
Their activity was tested determine the most efficient catalyst by
selecting the standard reaction conditions (ECH = 10 mmol, 120 °C,
1
of the reaction mixture was analyzed using H-NMR to determine the
conversion of epoxides.
Catalyst =0.02 mmol, 1 bar pressure of CO
revealed that the presence of electron-donating groups (−CH
], significantly enhances the organocatalyst activity for the
formation of cyclic carbonates compared to those with electron-with-
drawing groups, e.g.-F, and -NO . This behavior is quite expected and
2
, and 12 h). The results
3
) in
12 13 3 2
[C H N O
3
. Results and discussion
2
For industrial applications, designing an effective catalyst to gen-
can be explained based on the nucleophilicity of the triazole nitrogen,
where the presence of a carboxylic group on triazole moiety decreases
erate cyclic carbonate at ambient pressure is quite demandable in terms
of negative emission technology. This requires well-developed and easy
to synthesize homogeneous organocatalysts with excellent reusability
and recoverability bearing acidic/basic site and which mainly facilitate
its nucleophilicity, and decrease its ability to activate CO
2
molecule.
Thus, the presence of an electron-donating group such as three methyls
4

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
Fig. 3. Optimizing of the reaction conditions for the cycloaddition of CO
2
in the presence of epichlorohydrin. Conversion is based on 1H-NMR on the crude reaction
mixture.
on the phenyl moiety in catalyst A will significantly increase the elec-
tron density on the triazole ring and enhance its nucleophilicity. The
decrease of activity was observed, indicating the critical role of the
temperature (Fig. 3B). Increasing the catalyst to substrate ratio sig-
nificantly enhance the yield, whereas the maximum product (71 %
yield) is achieved using a catalyst-to- substrate ratio of 1:50 for 6 h at
120 °C (Fig. 3C). Therefore, the overall optimized reaction condition is
0.02 mmol of the catalyst, 2 mmol of the substrate, temperature
decreasing order in catalytic activity for cycloaddition reaction of CO
to epoxide is –mesitylene > phenyl > -F > -NO (Fig. 2). The NO
substituted compound exhibits a lower catalytic activity than the F-
2
2
2
-
substituted compound since NO
as compared to F. (Scheme 2)
2
is a more electron-withdrawing group
2
75−100 °C and time is 24−48 h under mild pressure of CO . A series of
Once the model catalyst was carefully chosen, then different para-
meters such as reaction time, temperature, and catalyst loading at a low
pressure of CO were explored. Increasing the reaction time played a
2
critical role in the formation of cyclic carbonate, with an increment of
time, a 100 % conversion within 24 h was obtained (Fig. 3A). Under
these reaction conditions at 120 °C, a complete synthesis of the ECH
carbonate product was received. However, at lower temperature a
epoxides were investigated towards the transformation of cyclic car-
bonates based on the obtained optimized reaction conditions. The
catalyst showed unusual activity for the epoxides bearing electron-
withdrawing substituents (Figure S10-S114, S16), as evidenced by the
conversion in 24 h. However, for substrates such as styrene oxide
(Figure S15) and 1,2 epoxy hexane (Figure S17), the conversion rises by
prolonging the reaction time (48 h) and clearly shows that such effect is
5

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
Scheme 3. Catalytic efficiency of catalyst A for chemical fixation of CO2/.
º
Reaction conditions: Catalyst 1 mol %, Pressure 1 bar, Time 24 h, Temperature 75 C.
,
#
º
, #
*
Temperature 100 C and * Time 48 h. Conversion determined by NMR.
due to the steric hindering during the reaction as shown in (Scheme 3).
It is worth noting that no side products were observed, hence the
catalyst gave > 99 % selectivity for the development of cyclic carbo-
nates. The catalyst was also investigated to its performances towards
internal epoxides, and unluckily the catalyst showed an inferior con-
version for internal epoxides using the optimized reaction conditions
that the catalyst retained its stability.
The mechanistic details are apprehended based on previously re-
ported literature for the catalytic cycloaddition of CO [51,53,59–61].
The nucleophilic hydroxyl group of the bifunctional catalyst might
activate the epoxide ring leading to the epoxy ring-opening through the
less hindered side and forming an oxy-anion species. In the next step,
the already formed catalyst-bound alkoxide ion acts as a nucleophile
2
(
Scheme 3).
Additionally, we applied the standard deviation (S.D) to investigate
and, in turn, activates CO
2
. as a result, closure of the ring will lead to
the mean and accuracy of the conversion data. Noticeably, each sub-
strate was tested three times to obtain data of S. D. ( ± 1 %) The
standard deviation was calculated using the following formula:
the formation of the final product i.e., cyclic carbonate.
4
. Conclusion
n
2
∑
(x
i
− x)
i=1
Standard Deviation =
In conclusion, we have successfully studied substituent effects n the
n − 1
triazole-ring on the catalytic activity for the construction of cyclic
carbonates. From the investigation, we observed that the catalytic ac-
tivity toward CO2 transformation significantly enhances with electron-
donating groups in [C12H13N O ]. The N-rich centers and the car-
boxylic functional group combined with electron donating substituent
assist in the cyclic carbonates synthesis, operating at ambient pressure
(1 bar) under solvent-free and cocatalyst free conditions. Significantly,
the catalyst is reusable, and more interestingly retained its stability
during the recycling. Therefore, the designed catalyst is highly vital to
fix CO2 into cyclic carbonates with attractive industrial importance.
Where
x
x
i
= Value of the ith point in the data set.
= Then mean value of the data set.
n = The number of data points in the data set.
3
2
On the bases of industrial importance, green and economic pro-
cesses, the reusability and, more significantly, the stability of the cat-
alyst play a vital role. The reusability and stability of catalyst A were
2
examined for the cycloaddition of CO into ECH using the optimal
º
conditions (1 mol % catalyst, 1 bar, 24 h, and 75 C). As the catalyst is
homogeneous, the catalyst was loaded once in the first run, afterward,
in each consecutive run, the precise amount of fresh substrate (ECH)
was added, to examine the reusability of the catalyst up to five runs. To
our delight, the catalyst possesses incredible reusability until five suc-
cessive runs to generate ECH carbonate (Figure S9 A). The catalyst was
successfully separated from the reaction mixture, using column chro-
matography, packed with silica and ethyl acetate/petroleum ether
mixture (1:3) as eluent. In this procedure, the cyclic carbonate is se-
parated first, followed by the desired catalyst. The catalyst is then re-
covered from the column, using methanol. Next, the recovered catalyst
was analyzed by 1H-NMR and FTIR (Figure S9 B, C), which indicates
CRediT authorship contribution statement
Suleman Suleman: Investigation, Writing - original draft. Hussein
A. Younus: Conceptualization, Methodology. Zafar A.K. Khattak:
Methodology. Habib Ullah: Investigation. Mirella Elkadi: Validation,
Writing - review & editing. Francis Verpoort: Conceptualization,
Writing - review & editing, Supervision.
6

S. Suleman, et al.
Molecular Catalysis 493 (2020) 111071
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ence the work reported in this paper.
[
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