Zn grafted covalent organic nanosheets (Zn@TpDT CONs) as

an efficient catalyst for the CO2 conversion to iodine-substituted

2-oxazolidinones

Submitted by
Gopal Kumar Shaw
Department of Chemistry, West Bengal State University
M.Sc. Chemistry
Reg No-1031811401035
Introduction
The dilemma arising from the excessive amount of CO2 (main
greenhouse gas) emission from the combustion of fossil fuel into the
environment needs to be mitigated due to CO2’s obvious negative
effect on the environment. Researchers around the globe have
focused on the design and development of CO2 capture, storage and
utilization technologies.
In this regard, among the various strategies of CO2 transformations, one of the
desirable and promising methods is the cyclization of propargylic amines with CO 2
to achieve five-membered heterocyclic compounds, widely known as 2-
oxazolidinones which can function as scaffolds for antimicrobial drugs or
antidepressants and in various organic syntheses.

To date, several homogeneous catalysts have been designed, synthesized and applied
to the CO2 fixation into propargyl amine to produce iodine-substituted 2-
oxazolidinones in presence of NIS, such as organic bases, organocatalysts,
quaternary phosphonium salts, quaternary ammonium salts, alkali metal salts,
transition metal complexes, N-heterocyclic carbene and ionic liquids.
 Heterogeneous Catalyst Superior Than Homogeneous Catalyst

Most of the catalyst was proved as an efficient catalyst for the CO2
conversion, but the issues are difficulty in separating the desired
product from the reaction mixture and limited thermal stability and
can’t be recycled and reused. Heterogeneous catalysts are superior to
homogeneous ones in terms of stability, separation and recyclability.
Several heterogeneous catalysts such as microporous organic
polymers, nitrogen-doped porous carbon monolith, modified molecular
sieves, ion-exchange resins, nanoparticles, metal oxides, poly (ionic
liquid), and supported catalysts have been developed. Among the
catalysts, transition metal decorated catalysts were proved to an
efficient one for the CO2 fixation under ambient conditions.
Experimental Section

Synthesis of TpDT CONs

‌ ,5-diamino-1,2,4-triazole
3 (45mg, 0.45mmol) and 1,3,5-
triformylphloroglucinol (90mg, 0.42mmol) were taken in a schlenk
tube and were dissolved in dioxane (3.0 mL). Dimethylacetamide
(1.0 mL) and mesitylene (3.0 mL) were poured into the tube and
allowed to stir until a greenish yellow color solution was appeared.
Following this aqueous acetic acid (1.0 mL of 6M) was carefully
added. The schlenk tube along with its contents was subjected to
place in oil bath for 3 days keeping the temperature at 120°C. The
mixture was subjected to cool to room temperature and reddish
brown precipitate was isolated by applying centrifugation techniques,
was washed with copious amount of hot DMF, dioxane, methanol,
acetone and THF, and was allowed to dry under vacuum to afford
TpDT CONs.
Synthesis of Zn@TpDT CONs
Initially, the as-synthesized CONs (1 g) and anhydrous ZnCl2 (0.1 g)
were taken in a RB flask containing 25 mL of ethanol. The RB flask
was fitted with a reflux condenser and was allowed to heat to 70 °C
for 10 h. Then, the mixture was cooled to normal temperature and
the resulting Zn-loaded CONs (Zn@TpDT CONs) was isolated by
applying centrifugation techniques and washed with ethanol to
eliminate unreacted ZnCl2 and ultimately, it was allowed to dry
under high vacuum conditions for 24 h at room temperature
(Scheme 1).
 Results and Discussion

FTIR ANALYSIS

The successful schiff base condensation reaction between a amine (3,5-diamino-2,4-

triazole) and an aldehyde (triformylphlorogucinol) was confirmed from FT-IR
spectra because of the disappearance of the characteristics carbonyl (-C=O)
stretching frequency at 1665 cm-1 and the C–H stretching frequency at 2909 cm-1
of triformyl phlorogucinol, and stretching frequency corresponding to the primary
amine at 3435 cm-1 of 3,5-diamino-2,4-triazole, depicted in Figure 1. The
appearance of the –NH str. (~3454 cm-1), -OH str. (3250 cm-1) and –C=N str.
(1604 cm-1) frequency also supports the condensation reaction. The clearly visible
peak corresponding to the enolic O-H and imine C-H suggest that the catalyst exist
mainly in enolic form not in enamine form.
Figure 1: Comparison FT-IR spectrum of the newly synthesized Zn@TpDT
CONs and the monomers.
Typical method for the synthesis of cyclic carbamates

N-Iodosuccinimide (1 mmol) was poured to a mixture of unsaturated

amine (1 mmol) and Zn@TpDT CONs (40 mg) in PEG-400 at room
temperature under exposure to 1 atm CO2. Then the solution was
allowed to stir for 12 h in the absence of light and allowed to quench
with an aqueous solution of sodium thiosulphate (20 mL, 1.0 M), and
extracted with the help of diethyl ether (4 × 25 mL). The combined
organic layer was then dried over anhydrous sodium sulphate and
concentrated in vacuum to afford the desired crude product which was
purified by silica gel column chromatography (eluent: petroleum
ether/ethyl acetate) to afford the desired cyclic carbamate, yield 96 %,
(Table 1, entry1).
Catalytic activity evaluation for cyclic carbamate
synthesis catalyzed by Zn@TpDT CONs

CO2 insertion into allyl amine as a model substrate facilitated by

Zn@TpDT CONs in the presence of NIS (iodinating agent) under the
atmospheric CO2 pressure in a polyethylene glycol (PEG) solvent at
room temperature for 10 h was tested. The desired iodine-substituted
2-oxazolidinones was successfully synthesized within 10 h which was
confirmed by NMR spectroscopy and the isolated yield was 96%
employing only 40 mg of Zn@TpDT CONs as a potential catalyst and
NIS (equimolar amount) under base-free conditions (entry 1, Table 1).
Inspired by the expected outcomes we have performed the reaction
with another substrate under same reaction condition and surprisingly
the expected desired product was achieved with 80% isolated yield.
Recyclability of the Zn@TpDT CONs catalyst
After each cycle the catalyst can be separate easily by applying centrifugation
techniques. The recovered catalyst was washed several times with copious amount
of water, methanol, and acetone, dried under vacuum. The consecutive run was
carried out under similar reaction conditions. The reused catalyst show excellent
catalytic activity up to five cycles without affecting its structural integrity. The
exception thermal and chemical stability of Zn (II) grafted CONs makes it highly
recyclable indicating heterogeneous nature of the synthesized material.
Conclusions:
1. A Zn(II)-grafted covalent organic nanosheets (Zn@TpDT
CONs) was established to be a highly potential catalytic
system for the adsorption of CO2 molecules, cycloaddition of
CO2 iodine functionalized 2-oxazolidinones under sustainable
conditions (base-free, atmospheric CO2 pressure and room
temperature).
2. For several unsaturated amines, Zn@TpDT CONs showcases
excellent catalytic activity. Of note, the catalytic system
retained its catalytic activity even after fifth cycle, which
renders the catalyst to be highly recyclable.
3. The synthesis of the low cost Zn(II)-loaded covalent organic
nanosheets and exploration of the CO2 fixation reaction under
sustainable conditions established in this study can unlock the
way to the construction of economical materials, which have
huge potential in both CO capture and fixation chemistry.
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Thank You