State-of-the-art catechol porphyrin COF catalyst for chemical fixation of carbon dioxide: Via cyclic carbonates and oxazolidinones

Article abstract of DOI:10.1039/c6cy00362a

A highly porous, crystalline catechol porphyrin COF was synthesized and applied as an organocatalyst for the chemical fixation of carbon dioxide to synthesize value-added chemicals such as cyclic carbonates and oxazolidinones under solvent-free and transition-metal-free conditions. The high surface area and the functionalities of the COF catalyst act synergistically to activate the starting material. The 2,3-DhaTph shows excellent activity towards cyclic carbonates at the atmospheric pressure of carbon dioxide. Additionally, this catalytic system is recyclable in nature and provides a higher turnover number than previously reported organocatalysts.

Full text of DOI:10.1039/c6cy00362a

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State-of-the-Art Catechol Porphyrin COF Catalyst for Chemical
Fixation of Carbon Dioxide via Cyclic Carbonates and
Oxazolidinones
Received 00th January 20xx,
Accepted 00th January 20xx
Vitthal Saptal,a Digambar Balaji Shinde,b Rahul Banerjee*b and Bhalchandra M. Bhanage*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
The highly porous, crystalline catechol porphyrin COF synthesized and applied as an organocatalyst for the chemical
fixation of carbon dioxide to synthesis value added chemicals such as cyclic carbonates and oxazolidinones under solvent
free and transition-metal free condition. The high surface area as well as functionalities of COF catalyst shows synergistic
effect to activates the starting material. The 2,3-DhaTph shows excellent activity towards cyclic carbonates at the
atmospheric pressure of carbon dioxide. Additionally, this catalytic system is recyclable in nature and provides high
turnover number than the previously reported organocatalysts.
field of catalysis,5 gas storage,6 opto-electronics7 and Sensing.8
Recently, published crystalline, porous, chemically stable
porphyrin based COFs (2,3-DhaTph and 2,3-DmaTph) have very
active catalytic sites such as acidic (catechol), basic
Introduction
(porphyrin). These functionalities make them highly active
organocatalyst for the organic transformations such as
tandem/cascade/one pot synthesis.5d Additionally, these COFs
are highly stable and crystalline in nature. We thought, the
integration of permanent porosity with separate antagonist
site with high surface area and high stability, of the 2,3-
DhaTph COF could be provide an excellent catalytic platform
for the fixation of carbon dioxide at the milder reaction
conditions.
Annually about 35 gigatonnes carbon dioxide (CO2) produced
and it covers up to 82 % of the total amount compared to
other greenhouse gases. Further increase of concentration of
CO2 will produce large and disorderly impact on environment.1
Although CO2 is considered as an alternative view as a
sustainable C1 source, its synthetic applications are limited
due to the low reactivity of CO2.2 Given their large applications
in the pharmaceutical and fine chemical industries the cyclic
carbonates synthesized form CO2 and epoxides has been
received intense attention.2b The synthesis of cyclic carbonates
and oxazolidinones from CO2 gives the 100% atom economical
reactions. Although various catalysts reported to synthesize
the cyclic carbonates, most of the processes demands harsh
reaction conditions like, use of transition metals, high
pressure, high temperature and separation problems.3 The
catalytic fixation of carbon dioxide at mild conditions remains
challenging, very few reports are available in the literature for
the synthesis of cyclic carbonates at mild conditions such as
low pressure as well as low temperature.3j-m
It is widely accepted that the catalyst bearing hydrogen bond
donor (HBD) has ability to accelerate the cycloaddition
reaction of CO2 with epoxides.9-18 In this illustration the
cooperative effect of HBD catalyst promote the ring opening of
epoxide by nucleophillic attack by an anion and stabilize the
oxyanion intermediate, the stabilized intermediate then
undergoes the attack of CO2 and yield the cyclic carbonates.18c
Recently, Sun et al. also demonstrated the computational
evidences for the synergistic effect of hydroxyl functional
group with epoxide for accelerating the rate of reaction
towards the synthesis of cyclic carbonates.22 The accelerating
effect of the HBD catalyst for this reaction using the
spectroscopic evidences also well known in literature.3k,9c,23
Herein we applied 2,3-DhaTph and 2,3-DmaTph COFs as an
organocatalyst for the chemical fixation of CO2 to synthesis the
cyclic carbonates and oxazolidinones. The 2,3-DhaTph bearing
HBD was found to be highly active, selective and recyclable
catalyst HBD for the chemical fixation of CO2 to cyclic
carbonates at the atmospheric pressure. Additionally, it is
worth mentioning that the developed COF catalyst provides
high turnover number and proceeds under solvent free as well
as transition-metal free condition.
Covalent Organic Frameworks (COF) are represents a special
emerging class of porous materials with pure organic group
and highly crystalline materials, with high surface area, formed
by using strongly covalent bonding between light weight
elements like C, N, B, Si and O with reticular network of
molecular building block.4 This material exhibits an exceptional
high surface area and uniform distribution of pore size and
high stability hence considered as promising material in the
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Results and discussion
Fig. 1 (a) Chemical structures of 2,3-DhaTph and 2,3-DmaTph COF (b) Thermogravimetric analysis 2,3-DhaTph (blue) 2,3-DmaTph (red), (c) PXRD analysis 2,3-DhaTph and 2,3-
DmaTph (d) N2 adsorption isotherm of 2,3-DhaTph (red) and 2,3-DmaTph (Blue).
The 2,3-DhaTph and 2,3-DmaTph were synthesized using
Table 1 Catalysts screening for the synthesis of cyclic carbonate.
previously reported method by
2,3-dihydroxyterephthalaldehyde
Schiff base reaction using
(2,3-Dha)/2,3-
O
O
O
O
COF
dimethoxyterephthalaldehyde (2,3-Dma) and a 5,10,15,20-
tetrakis(4-aminophenyl)-21H,23H-porphine (Tph) unit.5-d These
synthesized material characterized by using FT-IR, TGA, SEM,
BET and XRD techniques (Fig 1). Ensuring the high surface area
(~1000 m2 g-1 ESI-fig. 3), high thermal stability (fig. 1b) and the
presence of acid base nature of synthesized 2,3-DhaTph COF,
we applied this catalytic system for the cycloaddition reaction
of epoxide with carbon dioxide to synthesis the cyclic
carbonates. At the atmospheric pressure of CO2 the
cycloaddition reaction with styrene oxide (SO) to synthesis the
styrene carbonate (SC) was chosen as a model reaction using
COF catalysts and results are listed in Table 1. Without using
the catalyst and co-catalyst no any conversion of SO to SC was
observed (Table 1, entry 1), negligible yield of SC was observed
when the reaction carried out using only co-catalyst (Table 1,
entry 2). Next, we studied effect of solvent on reaction
condition, and we observed that the polar as well non-polar
solvents also accelerate the reaction effectively and gives
moderate yield (Table 1, entries 3-4). Next, we carried out the
reaction at the neat condition and it provides good yield of SC
using the TBAB as a co-catalyst (Table 1, entry 5).
CO2
Entry
COF (mmol)
Co-cat Solvent
Yield
(%)b
-
Sel.(%)b
TON
1
2
-
-
-
-
-
-
TBAB
TBAB
TBAB
TBAB
TBAB
TBAI
TBAI
KI
-
16
42
50
77
63
94
76
90
72
82
75
98
98
99
99
99
99
99
99
99
99
99
99
99
99
99
-
-
3
2,3-DhaTph
2,3-DhaTph
2,3-DhaTph
2,3-DmaTph
2,3-DhaTph
2,3-DmaTph
2,3-DhaTph
2,3-DmaTph
2,3-DhaTph
2,3-DmaTph
2,3-DhaTph
2,3-DhaTph
2,3-DhaTph
Catechol
PhMe
210
250
385
315
470
380
450
360
410
375
490
980
-
4
THF
5
-
-
-
-
-
-
-
-
-
-
-
-
6
7
8
9
10
11
12
13c
14 d
15
16e
KI
NaI
NaI
TBAI
TBAI
-
Traces
48
TBAI
99
120
a Reaction conditions: SO (10 mmol), COF (0.02 mmol), CO2 (1 atm.), Co-catalyst
(0.05 mmol), 110 °C for 12 h. b Determined by GC and GCMS. c CO2 (1 Mpa), 100
°C 4 h. d SO (20 mmol) 100 °C and 1 Mpa 4 h. e Catechol (0.04 mmol).
2 | J. Name., 2012, 00, 1-3
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hydrogen bond donor COF (2,3-DmaTph) were studied. Next,
we examined the effect of various co-catalysts such as TBAB,
TBAI, KI and NaI for the nucleophillic ring opening of epoxide,
using the both 2,3-DhaTph and 2,3-DmaTph catalyst system.
Among the various co-catalysts studied TBAI gives excellent
yield up to 94 % (Table 1, entry 7). Next, the comparative study
of 2,3-DhaTph and 2,3-DmaTph COFs as a catalyst have been
studied and we observed that the catalyst which bearing
hydrogen bond donor capability 2,3-DhaTph was more active
than the 2,3-DmaTph at the atmospheric pressure (Table 1,
entries 6-12). High selectivity towards the synthesis of cyclic
carbonates were observed (up to 99 %). In the next set of
experiments, reaction were carried out at the 1 MPa pressure
of carbon dioxide, increased yield of SC was observed (Table 1,
entry 13). The high TON of SC was observed when the reaction
Table 2 Various cyclic carbonates syntheses using the 2,3-DhaTph COF catalysts
O
2,3-DhaTph COF
O
O
O
CO2
TBAI (0.05 mmol), 110 oC
R
R
1 atm.
Yield: 94 %
TON: 470
Sel: >99
Yield: 90 %
TON: 460
Sel: >99
Yield: 95 %
TON: 475
Sel: >99
O
O
O
was carried out at
1 MPa pressure by increasing the
concentration of SO (Table 1, entry 14). Next, we observes that
the without using the co-catalyst (TBAI) negligible yield was
noted, TBAI needed for the nucleophillic ring opening of the
epoxide (Table 1, entry 15). Next, we the cycloaddition
reaction performed by using only catechol (1,2-benzenediol) as
catalysts and moderate yield of SC were observed (Table 1,
entry 16), thus we concluded that the presence of high surface
area of 2,3-DhaTph COF also plays crucial role for the
cycloaddition reaction. The high catalytic activity of 2,3-
DhaTph COF as compared to 2,3-DmaTph COF for chemical
fixation of CO2 should be mainly due to the presence of high
density of active sites with well oriented hydroxyl functional
group and porphyrin group together which could promote the
interactions between incoming substrates and active sites of
the COF to convert the product very effectively. Next, we
Yield 94 %
TON: 470
Sel: >99
Yield 93 %
TON: 460
Sel: >99
Yield 90 %
TON: 450
Sel: >99
O
O
O
O
O
O
Cl
Yield: 78 %
TON 390
Sel: >99
Yield: 84 %
TON 420
Sel: >99
Yield: 88 %
TON: 440
Sel: >99
a Reaction Conditions: Epoxide (10 mmol), CO2 (1 atm.) 2,3-DhaTph (0.02 mmol),
TBAI (0.05 mmol), 110 °C, 12 h. Yield and selectivity calculated by GC.
Thus, we concluded that the solvents are not necessary for this
reaction. Encouraged by these results, the comparative study
of hydrogen bond donor COF (2,3-DhaTph) and without
observed
that
the
catalyst
Fig. 2 (a) effect of amount of loading of COF catalyst, (b) effect of temperature, (c) effect of reaction time, (d) recycle study of COFs, (e) SEM image of 2,3-DhaTph and (f) SEM
images of 2,3-DmaTph COF before and after the cycloaddition reactions.
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loading for the cycloaddition reaction at the atmospheric
pressure of carbon dioxide plays the key role to provide the
high yield and TON, as the loading of catalyst decreases yield
also decreases, 0.02 mmol of catalyst loading is optimum
loading to achieve the highest conversion (Fig. 2a). Next, we
studied the effect of temperature; 110 °C is the effective
temperatures to achieve highest conversion of SC, as the
temperature of reaction system decreased the decreased
amount of SC were observed (Fig. 2b). After this we studied
the effect of time on reaction condition and it was observed
that the 12 h was optimum time to achieve the highest
conversion of SC, further increase of time was not effective
(Fig. 2c).
After the optimization conditions in hand, a variety of
substrates were tested under the optimized reaction condition
to synthesize the cyclic carbonates (Table 2). In substrate
study, it was observed that the developed catalytic system is
applicable for the synthesis of various cyclic carbonates
Table 3 Synthesis of oxazolidinones using 2,3-DhaTph COF as a catalyst system
Fig.3 Comparatives IR data 2,3-DhaTph and 2,3-DmaTph COF catalyst.
O
O
O
N
N
N
O
2,3-DhaTph, TBAI
2 Mpa
R
CO2
TBAI
O
1
2
3
H
O
H
O
Entry
Oxazolidinones
Time
Yield
(%)b
39
Regio-
sel.c
TON
NH
N
HN
N
NH
N
HN
N
N
1d
2
2
2
2
3
1
3
98:2
98:2
97:3
195
355
480
N
71
O
3
96
O
O
R
N
N
4
5
3
97
93
59
86
96
92
97:3
98:2
99:1
98:2
99:1
99:1
485
465
295
430
480
460
N
N
I
O
R
O
O
H
H
OH
O
O
OH
O
R
I
O
R
I
3
O
N
CO2
O
O
Ph
O
H
O
H
O
NH
N
HN
N
NH
N
HN
N
6e
12
15
8
N
N
7
Fig.4 Proposed reaction mechanism for the synthesis of cyclic carbonates from carbon
dioxide and epoxide catalysed by 2,3-DhaTph COF as a catalyst system.
8
including aliphatic as well as aromatic carbonates. The cyclic
aliphatic carbonates are also well tolerated. It is worth
mentioning that, the epoxides with aromatic substituent like
styrene oxide and functional styrene oxide like Cl, F and Br
gives the high yield and turnover number as compared to the
aliphatic epoxides.
O
9
8
O
N
O
Ph
a Reaction conditions: Aziridines (5 mmol), 2,3-DhaTph (0.01 mmol), TBAI (0.05 mmol),
CO2, 2 Mpa, 50 °C . b Determined by GC and GC MS. Molar ratio 2 to 3 by GC. d 1
c
To prove the HBD catalysis by using the 2,3-DhaTph we carried
out the FT-IR spectroscopy and NMR (ESI-Fig. S-8) by using the
1,2-benzendiol. The comparative IR spectra of epoxide
e
Atm. pressure CO2. 80 °C.
4 | J. Name., 2012, 00, 1-3
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(epichlorohydrin) and reference HBD catalyst as 1,2- Based on the reported method for the cycloaddition reaction
benzenediol were taken (Fig. 5). Initially, the 1,2-benzenediol of CO2 with epoxide promoted by HBD catalysis9-18,22 we have
showing two sharp peak (~3300-3400 cm-1), the mixture of developed a tentative mechanism using the 2,3-DhaTph COF
epichlorohydrin and 1,2-benzenediol gives the broad peak as a catalyst system (Fig. 4). The presence of vicinal catecholic
(3389.85 cm-1). This broad peak clearly indicates the presence group of 2,3-DhaTph COF helps to polarize the C-O bond of
of hydrogen bonding between 1,2-benzenediol and epoxide.
epoxide16b,22 using the hydrogen bonding which subsequently
attacked by the anion generated from the co-catalyst to open
the epoxide ring. The opening of epoxide ring generates the
oxyanion intermediates which also stabilized by hydrogen
bonding of the catecholic group of 2,3-DhaTph COF. Next, the
oxyanion intermediate adds the carbon dioxide molecule and
fallow the subsequently cyclization to from cyclic carbonate.
Hence, we concluded that the presence of 2,3-DhaTph catalyst
with high surface area showing the accelerating effect for the
cycloaddition reaction of epoxides with carbon dioxide.
As the 2,3-DmaTph COF showing the high activity towards the
synthesis the cyclic carbonates we checked the co-operative
effect of 2,3-DhaTph (hydrogen bond donor) catalyst and co-
catalyst by using the hot filtration method.20 To check the
leaching study of 2,3-DhaTph COF catalyst we followed the
method reported by He.20b The cycloaddition reaction of SO to
SC was investigated at the optimized reaction condition, after
6 h the reaction mixture was hot filtered and resultant
reaction mixture kept for the further reaction. The reaction
mixture analysed after every two hour by GC negligible
amount increased conversion were noted this may be due to
the dissolved TBAI in reaction mixture. (ESI-Fig-S6). The hot
filtered mixture then evaporated on SEM holder5e and
analysed by using the EDS, I and N elements were detected
(ESI, S-13). Next, to study the leaching of COF same
experiment was performed without using co-catalyst (TBAI)
and reaction mixture evaporated on SEM holder for elemental
analysis, the N element was not detected hence, we concluded
that there is no leaching of 2,3-DhaTph in to the reaction
mixture while, the co-catalyst (TBAI) leached (leached co-
catalyst also detected by using the GC-MS). and no leached
amount of 2,3-DhaTph were noted.
Fig. 5 IR spectroscopic evidences for HBD promoted reactions
After such encouraging results for the synthesis of cyclic
carbonates we further extended this protocol for the synthesis
of oxazolidinones by coupling of CO2 with aziridines (Table 3)
using the 2,3-DhaTph as a catalyst system. Oxazolidinones are
the most important class in the field of chiral auxiliaries,
synthetic and medicinal chemistry.19 Various 1-alkyl-2-
arylaziridines were synthesized and applied for the synthesis of
5-aryl-2-oxazolidinones at low temperature and moderate
pressure using the 2,3-DhaTph COF as a catalyst system under
solvent free condition. The carboxylation reaction of carbon
dioxide with 1-methyl-2-phenylaziridine (1) to 3-methyl-5-
phenyloxazolidin-2-one (3) was investigated as model reaction.
At the atmospheric pressure of carbon dioxide the low yield of
3 was noted (Table 3, entry 1), thus we performed reaction at
the high pressure, good yield of the 3 observed for the 1h of
time (Table 1, entry 2). Excellent yield and selectivity was
observed when reaction performed for 3h. Aziridines
substituted with aliphatic amine group provides excellent yield
as well as the regioselectivity (Table 3, entries 3-5), while the
bulky aziridines provide poor yield, by increasing the time and
temperature of the reaction system gives moderate yield
(Table 3, entry 6). Cyclic aziridines including aliphatic as well as
aromatic also found to reactive and provide high TON (Table 3,
entries 7-8). The yield and turnover number for the synthesis
of oxazolidinones using 2,3-DhaTph was also high at the milder
temperature and moderate pressure of carbon dioxide.
Additionally, the 2,3-DhaTph COF provides the excellent
regioselectivity towards the synthesis of 5-aryl-2-
oxazolidinones under mild and solvent free reaction
conditions.
A significant advantage of any porous heterogeneous catalyst
is that they could be conveniently recycled and reused21 To
investigate the recyclability of the developed COF catalyst the
cycloaddition reaction of SO to SC were performed at the
optimized reaction conditions and we observed that the 2,3-
DhaTph COF catalyst could be recycled up to five consecutive
recycle without loss of its catalytic activity(Fig. 2d), for each
recycle fresh amount of TBAI were added along with 2,3-
DhaTph COF. The slightly decreased yields of carbonates for
each cycle were noted this may be due to handling loss of
catalyst. After the fifth recycle the catalyst were characterized
using the SEM (Fig. 2e and f) and FT-IR analysis (fig. 3) no any
significant structural changes were observed. The higher
catalytic activity of 2,3-DhaTph over 2,3-DmaTph for the
synthesis of cyclic carbonates were may be due to the unique
structural features of the 2,3-DhaTph such as presence of high
surface area with abundant HBD ability. The high surface area
with abundant HBD of 2,3-DhaTph helps activate the epoxide
as well as the porphyrin group helps to adsorb the carbon
dioxide molecule effectively.
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13056; d) S. Kandambeth, V. Venkatesh D. B. Shinde, S.
Kumari, A. Halder. S. Verma, & R. Banerjee, Nat. Chem. 2015,
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Conclusions
In conclusion, we have developed a highly efficient catalytic
method for the synthesis of cyclic carbonates as well as
oxazolidinones by cycloaddition reaction using the 2,3-DhaTph
and 2,3-DmaTph COF as a catalyst for the first. The developed
COF represents high surface area with abundant hydrogen
bond donor ability, which helpful for the activation of epoxide
and carbon dioxide. This catalyst system demonstrates the
high TON for the synthesis of cyclic carbonate as well as
synthesis of oxazolidinones with high regioselectivity. The
catalyst could be recycled for five consecutive recycle runs as
well as proceeds under solvent free and metal free conditions.
Efforts are underway to develop more environmentally benign
catalyst for fixation of carbon dioxide at ambient conditions.
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Acknowledgements
Author (VBS) gratefully acknowledges to the University Grant
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State-of-the-Art Catechol Porphyrin COF Catalyst for Chemical
Fixation of Carbon Dioxide via Cyclic Carbonates and
Oxazolidinones
Vitthal Saptal,a Digambar B. Shinde,b Rahul Banerjeeb* and Bhalchandra M. Bhanagea*
a* Department of Chemistry, Institute of Chemical Technology (Autonomous), Matunga, Mumbai, 400 019, India.
b* Physical/Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune.
411008, India.