Basic Salt-Lake Brine: An Efficient Catalyst for the Transformation of CO2 into Quinazoline-2,4(1 H,3 H)-diones

Article abstract of DOI:10.1002/cssc.201802431

The efficient transformation of CO₂ into value-added chemicals with green, abundant, and cheap catalysts is an interesting and challenging topic in both green and sustainable chemistry. In this study, a series of salt-lake brines were used for the first time to catalyze the reaction of CO₂ and a broad range of 2-aminobenzonitriles to form the corresponding quinazoline-2,4(1 H,3 H)-diones. It was found that the abundant, available, and inexpensive Zhabuye basic salt-lake brine could efficiently promote the reaction of 2-aminobenzonitriles under low pressure of CO₂. Very high yields of value-added products were obtained. Further studies indicated that the basic carbonate and borate ions in the brine play key roles in accelerating the reactions.

Full text of DOI:10.1002/cssc.201802431

Accepted Article
Title: Basic Salt Lake Brine: Efficient Catalyst for the Transformation of
CO2 into Quinazoline-2,4(1H,3H)-diones
Authors: Jiayin Hu, Shangqing Chen, Yafei Guo, Long Li, and Tianlong
Deng
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10.1002/cssc.201802431
ChemSusChem
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Basic Salt Lake Brine: Efficient Catalyst for the Transformation of
CO2 into Quinazoline-2,4(1H,3H)-diones
Jiayin Hua*, Shangqing Chena, Yafei Guoa, Long Lia and Tianlong Denga,b*
[13]
Abstract: The efficient transformation of CO2 into value-added
chemicals with green, abundant and cheap catalysts is an interesting
and challenging topic in both green and sustainable chemistry. In
this work, a series of salt lake brines were used for the first time to
catalyze the reaction of CO2 and a broad range 2-aminobenzonitriles
to form corresponding quinazoline-2,4(1H,3H)-diones. It was found
that the abundant, inexpensive and available Zhabuye basic salt
lake brine could efficiently promote the reactions of 2-
aminobenzonitriles under low pressure of CO2, and very high yields
of value-added products were obtained. Further study indicated that
the basic carbonate and borate ions in the brine play key roles in
accelerating the reactions.
butylammonium)[12], and metal-base MgO-ZrO2
are reported
to catalyze this reaction. However, the scopes of these
methodologies are often limited by the requirement for
specialized additives and the presence of organic and toxic
solvents. In addition, several kinds of task-specific ionic liquids
were proved to be efficient catalysts for this reaction[14], but they
are expensive and difficult to synthesize. Particularly, Ma and
co-workers found water can promote the reaction of CO2 and 2-
aminobenzonitriles without any additive. This is an extremely
green and simple route to synthesize quinazoline-2,4(1H,3H)-
diones[15]. However, the reaction conditions was somewhat
harsh, especially need very high CO2 pressure (Scheme 1a).
Salt lakes, which are distributed in the worldwide scale,
have been considered as the store house of mineral salts,
containing almost inexhaustible mineral resources including
potassium, lithium, boron, sodium, magnesium and other
chemical elements[16]. Researches on salt lake brines are mainly
concentrated on the extraction of these valuable and scattered
elements[17]. However, as far as we know, there is no report on
using these green, abundant and easily available salt lake brines
as catalysts.
Introduction
Carbon dioxide (CO2) is promising C1 feedstock for green
and sustainable chemistry[1]. Transformation of this abundant,
nontoxic, nonflammable and renewable C1 source into value-
added chemicals by catalysis has drawn increasing attention[2].
Efficient catalysts, such as homogeneous metal complexes[3],
heterogenetic metal-base materials[4] and metal-free catalysts
including organic and inorganic base[5], ionic liquids[6], N-
heterocyclic carbenes[7], have been used for the chemical
fixation of this thermodynamically stable molecule. Although
many efforts have been made, very green, abundant and cheap
catalyst that is capable of promoting the transformation of CO2 is
still highly desirable and challenging.
Quinazoline-2,4(1H,3H)-diones and their derivatives are an
important class of heterocyclic compounds with wide range of
biological and pharmacological activities[8]. The atom-economic
reaction between CO2 and 2-aminobenzonitriles is an excellent
route to quinazoline-2,4(1H,3H)-diones. Up to now, significant
works have been proposed and various catalysts have been
used for the synthesis of quinazoline-2,4(1H,3H)-diones. For
instance, organic and inorganic base including 1,8-
Scheme 1. Synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and 2-
aminobenzonitriles a) in water (B. X. Han et al. 2013[15]) and b) in brine (this
work).
diazabicyclo[5.4.0]undec-7-ene[9],
1,1,3,3-tetramethyl
TBA2[WO4] (TBA=tetra-n-
Herein, in this work, a series of basic salt lake brines were
used for the first time to catalyze the reaction of CO2 and a
broad range 2-aminobenzonitriles to form corresponding
quinazoline-2,4(1H,3H)-diones, as shown in Scheme 1b. It was
found that the abundant, inexpensive and available basic salt
lake brines could efficiently promote the reactions of 2-
aminobenzonitriles at low pressure of CO2, and high yields of
value-added products were obtained. The mechanism
exploration demonstrated that the basic carbonate and borate
ions in the brines play key roles in accelerating the reactions.
[11]
guanidine[10]
,
Cs2CO3
[a]
[b]
Dr. J. Hu, S. Chen, Y. Guo, L. Li, Prof. T. Deng
College of Chemical Engineering and Materials Science
Tianjin University of Science and Technology
No. 29, 13 Avenue, TEDA, Tianjin, China
E-mail: hujiayin@tust.edu.cn; tldeng@tust.edu.cn
Prof T. Deng
College of Marine and Environmental Science
Tianjin University of Science and Technology
No. 29, 13 Avenue, TEDA, Tianjin, China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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Results and Discussion
Table 1. Chemical composition of salt lake brines used in this work.
Ion Concentrations (mg/L)
Entry
Brine (Salt Lake)
2-
2-
Na+
K+
Ca2+
Mg2+
Li+
Cl-
SO4
Borate
CO3
1[18]
2[19]
3[20]
4[21]
5[22]
6[23]
7[24]
8[25]
Zhabuye a
Searles b
129600
183132
54130
84888
17777
82613
40130
90772
40900
457.8
7320
--
--
1170
--
156200
149277
67670
38600
54939
--
11000
--
44200
--
409.6
--
28072
Dangxiongcuo c
Da Qaidam d
Atacama e
--
--
2910
2650
777
--
10800
6265
--
19674
11111
27004
57500
23990
--
181927
174444
269477
235647
185903
32578
21111
41700
42630
50843
--
--
--
--
--
19888
10208
3245
--
--
1777
--
West Taijnar f
Gas Hure g
13930
--
--
--
East Taijnar h
14976
--
--
The salt lake brines used in our experiments were readily
prepared by mixing the corresponding salts according to the
reported composition of brines[18-25] which were from the salt lake
in Zhabuye, Searles, Dangxiongcuo, Da Qaidam, Atacama,
West Taijnar, Gas Hure and East Taijnar, respectively, and the
chemical compositions of different brines were shown in Table 1.
This suggests that the main cations in brines are Na+, K+ and
Mg2+, especially, Gas Hure salt lake brine has Ca2+ and Li+ can
be found from Zhabuye and Atacama salt lake. The main anions
Table 2. Reaction of CO2 and 2-aminobenzonitrile (1a) in various catalyst
systems.[a]
Catalyst[b]
pH
Yield[d](%)
2-
2-
in brines are Cl- and SO4 while borate and/or CO3 can be
found in Zhabuye, Searles, Dangxiongcuo, Da Qaidam and
Atacama salt lake.
Entry
1
2
Water
6.629
9.694
9.984
9.658
7.136
7.418
6.050
5.381
4.875
9.732
9.816
0
98
54
34
6
Initially, to test the catalytic activity of various brines with
different composition, the conversion of CO2 and 2-
aminobenzonitrile (1a) to quinazoline-2,4-(1H,3H)-dione (2a)
a
3
b
o
was used as a model reaction at 1 MPa CO2 and 140 C, and
4
c
the results are given in Table 2. The reaction did not occur in
water (Table 2, entry 1), and the result was corresponding with
the reported work[15]. Interestingly, the salt lake brines showed
different efficiency for this reaction, and the yields of the target
product quinazoline-2,4-(1H,3H)-dione (2a) were in range from 0
to 98% in 8 h (entries 2-9). A great boundary of these salt lake
brines is the pH, which was crucial for the occurrence of the
reaction. The salt lake brines containing all cations include Na+,
K+, Mg2+, Ca2+ and Li+ as well as anion Cl- and SO42- with the pH
value less than 7 had no catalyst activities for this reaction.
However, the salt lake brines with the pH value more than 7, i. e.
basic salt lake brines can promote the reaction of CO2 and 2-
5
d
6
e
2
7
f
0
8
g
0
9
h
NaOH solution
a’
0
10
11[c]
0
96
aminobenzonitrile (1a). A main difference of these acidic and
[a] Reaction conditions: 1a (2.0 mmol, 0.2643 g), CO2 (1.0 MPa),
aqueous solution catalyst (3 mL), 140 oC, 8 h. [b] The catalysts in entries
2-9 corresponds to the entries 1-8 in Table 1. [c] The brine was from
Zhabuye salt lake after filtering to remove impurities. [d] Isolated yield.
2-
basic salt lake brines is the employ of borate and CO3
.
Moreover, the yield of 2a was increased with the increasing of
the concentrations of borate and CO32-, and the Zhabuye basic
salt lake brine with pH value 9.694 showed the highest efficiency
for this reaction, and the yield of the target product 2a was 98%.
The activity of NaOH solution whose pH value was 9.732 was
also screened, but this inorganic base had no activity for the
reaction (entry 10). From the above findings, it could be
2-
inferred that the anion borate and CO3 could affect the pH
value of the salt lake brines, as well as the catalyst activity.
2-
In other words, both the borate and CO3 of the salt lake
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brines played important role in the basic salt lake brines
promoted reaction of CO2 and 2-aminobenzonitrile. In
addition, instead of the synthetic brine, the salt lake brine
reaction over the Zhabuye basic salt lake brine were also
tested, and the results are given in Figure 2. As expected,
the yield of 2a increased with the increasing of the CO2
pressure (Figure 2a). The time profile of the conversion of
1a by 3 mL Zhabuye basic salt lake brine (Figure 2b) was
also tested and 1a could be completely converted with the
increasing of the time. It was found that a yield of 98% could
be achieved in 8 h, namely the reaction reached equilibrium
and almost all reactant 1a was transformed in the relatively
short time.
2-
from Zhabuye lake that contained 35600 mg/L CO3 and
8230 mg/L borate was taken to catalyze this reaction after
simple filtering to remove impurities, and the result was
given in the entry 11, Table 2. It can be seen that the salt
lake water sample showed similar catalyst activity with our
synthetic brine with 96% yield of 2a, and this result inferred
the synthetic brines we used could represent the real salt
lake brines.
The results above showed that Zhabuye basic salt lake
brine could promote the reaction effectively. We further
studied the effect of Zhabuye basic salt lake brine dosage
and the dependence of the yield of 2a on amount of
Zhabuye basic salt lake brine a was given in Figure 1. The
isolated yield of 2a increased with increasing Zhabuye basic
salt lake brine dosage at beginning, and a yield of 98%
could be achieved when 3 mL Zhabuye basic salt lake brine
used. No further increase in the yield was observed with
increased Zhabuye basic salt lake brine dosage, suggesting
that all the reactant was transformed with 3 mL Zhabuye
basic salt lake brine.
Figure 2. Reaction conditions: 1a (2.0 mmol, 0.2643 g), 140 oC, Zhabuye
basic salt lake brine (3.0 mL), different CO2 pressure and reaction times,
respectively. Isolated yield. a: Dependence of the yield on different CO2
pressure. b: The time profiles of the conversion of 1a with different reaction
times.
The results above showed that Zhabuye basic salt lake
brine could promote the reaction effectively at 1 MPa CO2
pressure and within 8 h. We further studied the effect of reaction
o
o
temperature ranging from 100 C to 150 C on the yield of 2a
(Figure 3). It was shown that the yield of the product depended
strongly on the reaction temperature in the lower temperature
o
region. The yield reached 98% at 140 C, but the yield of 2a
decreased when the temperature increased to 150 oC. The
possible reason maybe that the reaction was an exothermic
reaction and the reaction was inhibited by higher temperature.
Figure 1. Dependence of the yield on amount of Zhabuye basic salt lake
brine. Reaction conditions: 1a (2.0 mmol, 0.2643 g), CO2 (1.0 MPa), 140
oC, 8 h, different Zhabuye basic salt lake brine dosages. The yield was
isolated yield.
In addition, considering many salt lake brines had very
high salinity, the concentration of Zhabuye basic salt lake
brine was reduce by half, and the catalyst activity of this
reduced brine with different dosage for the reaction of CO2
and 2-aminobenzonitrile (1a) to quinazoline-2,4-(1H,3H)-
dione (2a) was given in Table S1. When 3 mL Zhabuye
basic salt lake brine with reduced concentration was used
as catalyst, the yield of 2a was 88% (Table S1, entry 1),
which was not considerably lower than that catalyzed by
Zhabuye basic salt lake brine (98%, Table 2, entry 2). This
result inferred that reduced the concentration of brine
appropriately could effectively decrease the salinity of the
brine but not affect its catalyst activity notably.
Figure 3. Dependence of the yield of 2a on temperature. Reaction conditions:
1a (2.0 mmol, 0.2643 g), CO2 (1 MPa), Zhabuye basic salt lake brine (3.0 mL),
8 h, different reaction temperature. Isolated yield.
After the reaction, the Zhabuye basic salt lake brine can
be separated by centrifugation and reused directly for the
next run. The reusability of Zhabuye basic salt lake brine
The effect of CO2 pressure and reaction time on the
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was tested, and the results are shown in Figure 4. The
catalyst activity of the Zhabuye basic salt lake brine did not
change notably after being reused five times, showing the
reusability of this Zhabuye basic salt lake brine.
the substrate could be completely converted within 7 h (2b), As
R were halogen with some electron-withdrawing effects, a much
longer time were needed to complete the reaction (2c-2e).
2-
As discussed above (Table 2), the borate and CO3 played
important role in the basic salt lake brines promoted reaction of
CO2 and 2-aminobenzonitrile. In order to clarify the roles of
these anion, Firstly, we studied their effects on the reaction,
respectively, and the results are given in Table 4. The pKa
values of the anion conjugate acid in water were in range form -
6.1 to 12.47, indicated the basicity of the anions were in the
2-
2-
order B4O72- > CO3 >SO4 >Cl-, which agreed with the catalyst
2-
activity of the anions. The B4O7 with strongest basicity can
efficiently catalyze this reaction with high yield of 2a (Table 4,
entry 7). Combining the related knowledge in the literature[26]
,
these results inferred that the catalyst activity of the anion is
2-
determined by the basicity of the anion. In addition, CO3 may
also provide C1 source to react with 2-aminobenzonitrile,
2-
therefore, the reaction of salt solution containing CO3 with 2-
aminobenzonitrile was proceeded without introducing CO2, and
this reaction did not occur (Table 4, entry 4). We also carried out
the experiments by adding labeled 13CO2 instead of CO2 (entries
5-6 in Table 4), and the same 13C NMR spectras were obtained
(seeing in the supporting information). The 13C NMR spectra
showed an obvious peak at 150.77 parts per million, which can
be attributed to the product 2a. These results above inferred the
C1 source that reacted with 2-aminobenzonitrile was from CO2
only, and the borate and CO32- played similar role.
Figure 4. Recyclability of the Zhabuye basic salt lake brine. Reaction
conditions: 1a (2 mmol, 0.2643 g), Zhabuye basic salt lake brine (3 mL),
CO2 (1 MPa), 140 oC and 8 h.
Table 3. Synthesis of various quinazoline-2,4(1H, 3H)-diones 2a-2e.[a]
Entry
Substrate
Product
T (h)
Y[b] (%)
Table 4. Reaction of CO2 and 2-aminobenzonitrile (1a) in pure salt
solutions[a]
1
8
98
Entry
1
Anion[b]
Cl-
pKa of Conjugate Acid [c]
Yield[f] (%)
-6.10
1.99
0
0
2
3
7
97
98
2-
2
SO4
2-
3
CO3
10.33
10.33
12.47
12.47
12.47
47
0
24
4[d]
5[e]
6[e]
7
CO3
2-
2-
CO3
48
94
94
2-
B4O7
4
5
16
30
96
98
2-
B4O7
[a] Reaction conditions: 1a (2.0 mmol, 0.2643 g), CO2 (1.0 MPa),
aqueous solution catalyst (3 mL), 140 oC, 8 h. [b] Concentrations of
Na2CO3 and Na2B4O7 were approximate 20000 mg/L. [c] Values were
taken from the pKa table of Lange’s Handbook of Chemistry, 13th
edition. [d] The reaction was proceeded without CO2. [e] Lbeled 13CO2
was used instead of CO2. [f] Isolated yield.
[a] T=Time, Y=Yield. Reaction condition: Substrate (2.0 mmol), CO2 (1
MPa), Zhabuye basic salt lake brine (3.0 mL), 140 oC. [b] Isolated yield.
The reactions of 1 MPa pressure CO2 with a range of
different substituted substrates were then conducted in the
Zhabuye basic salt lake brine catalyst. The optimized reaction
times, the isolated yields are summarized in Table 3. In general,
2-aminobenzonitrile with different substituents were effective
substrates to give the corresponding carbonates 2a-2e in
excellent yields. It appears that the reaction is sensitive to the
electronic effect of substituted R. When R was methoxy group,
2-
In order to further clarify the roles of CO3 and borate with
2-aminobenzonitrile, series of NMR spectroscopic experiments
were carried out using 2-aminobenzonitrile interacted with pure
H2O, CO3 and borate solution at 140 C for 8 h without CO2,
respectively. It was found the 1H signal of NH2 in 1a was a sharp
single peak (Figure 5a). This result might suggest that pure H2O
2-
o
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alone could not activate the NH2 from 2-aminobenzonitrile, and
therefore the transformation of CO2 was not proceeded, which is
consistent with the experimental result that the reaction did not
1
occur with water (entry 1 in Table 2). However, the H signal of
NH2 in 1a was changed into a broad peak and shifted obviously
2-
2-
when CO3 was added (Figure 5b), which indicate that CO3
could activate the NH2 and promote the next transformation of
2-
CO2. While the B4O7 with stronger basicity and higher catalyst
1
activity for the reaction was added, the H signal of NH2 in 1a
was disappeared (Figure 5c). The 1H NMR spectroscopic
experiments revealed that the H in NH2 was more likely to be
activated by a strong base, i.e., the 1H NMR spectroscopic
experiments further proved the basicity of the catalyst played a
key role in this reaction.
Scheme 2. The possible mechanism for the basic salt lake brine-promoted
reaction of CO2 with 2-aminobenzonitrile.
Conclusions
In conclusion, we have developed a new strategy to utilize
basic salt lake brine as catalyst to effectively promote the
reactions of CO2 and 2-aminobenzonitrile substrates under mild
CO2 pressure to form very high yields of quinazoline-2,4(1H,3H)-
Figure 5. 1H NMR spectrum of 1a (2 mmol) with a) water b) Na2CO3 (0.5 mmol)
solution, c) Na2B4O7 (0.5 mmol) solution. Experiment condition: 1a (2.0 mmol,
0.2643 g), water, Na2CO3 (0.5 mmol), or Na2B4O7 (0.5 mmol) solution (3 mL),
140 oC, 8 h. After the reaction, 0.05 mL reaction mixture was added into the
DMSO-d6 (0.6 mL) to carry out the 1H NMR spectroscopic experiments.
2-
diones. The B4O72- and CO3 anions contained in the basic salt
lake brine play key roles in the activation of both CO2 and 2-
aminobenzonitrile. As green, abundant, diversified and cheap
aqueous resources, salt lake brines with different acid-base
properties contain various functional ions, such as alkali metal
ions, alkali-earth metal ions, halide ions, borate ion, carbonate
ion and so on. We hope that this greener route can provide
ideas and methods for the further applications of the salt lake
brines in catalyst.
Therefore, on the basis of the experimental results of this
work, and the related knowledge in the literature[27], a possible
mechanism for the basic salt lake brine promoted the reaction of
CO2 is proposed, which is shown in Scheme 2. For the first step,
when CO2 was added into the basic salt lake brine, the anion
with strong basicity could interact with the acid carbon of the
CO2, that was why the reactions could proceed with mild CO2
pressure. At the same time, the hydrogen atom of the amino
group was activated by the anion from basic salt lake brine, so
the electrophilic attack of CO2 on the amino group is more
favorable. After this step a conjugate acid HX- and the
carbamate anion are formed. This step may be the rate-limiting
step of the reaction, the catalyst with stronger basicity can
enhance this step, as well as the reaction. Then, an
Experimental Section
Materials: CO2 was supplied by Tianjin Feilin Gases Co., Ltd with a
purity of 99.99%. 13CO2 was supplied by Beijing Gaseous Chemical Gas
Center. 2-Aminobenzonitrile (98%) and 2-Amino-5-chlorobenzonitrile
(98%) were obtained from 3A chemicals Ltd. 2-Amino-4-
chlorobenzonitrile (99%) was purchased by Tokyo Chemical Inorganic
Co., Ltd. 2-Amino-4,5-dimethoxybenzonitrile (99%) was purchased by
Fluorochem Ltd. 2-Amino-5-bromobenzonitrile (99%) was supplied by J &
K Scientific Ltd. The inorganic salts used to prepare the brines were from
Sinopharm Chemical Reagent Co., Ltd and of standard analytical grade.
All the chemicals were commercialized and without further purification.
intramolecular nucleophilic cyclization and subsequently
a
rearrangement occur to form a quinazolide anion. According to
the reference[27b], the pKa of the quinazoline-2,4(1H,3H)-dione is
14.7, which inferred the basicity of quinazolide anion is stronger
Preparation of Salt Lake Brines: In briefly, according to brine
composition in reference, the appropriate quantity of salts was mixed
together to prepare a series of artificially synthesized brines. The
concentration of cation in the artificially synthesized brines, such as
sodium ion, potassium ion, calcium ion and so on, was measured by
inductively coupled plasma optical emission spectrometer (ICP-OES,
Prodigy, Leman Co., America) with an uncertainty of ± 0.005 in mass
2-
than both B4O72- and CO3 anions. Therefore, in the last step,
the quinazolide anion extract the proton from HX- to form the
target product, and the basic anion can recover for the second
cycle.
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fraction. The concentration of Cl- in the artificially synthesized brines was
measured in triplicate by titration with a standard solution of Hg(NO3)2 in
the presence of ten drops of mixed indicator (diphenylcarbazone,
[5]
[6]
[7]
[8]
C. D. Gomes, O. Jacquet, C. Villiers, P. Thuery, M. Ephritikhine, T.
Cantat, Angew. Chem. Int. Ed. 2012, 51, 187-190.
J. Y. Hu, J. Ma, Q. G. Zhu, Z. F. Zhang, C. Y. Wu, B. X. Han, Angew.
Chem. Int. Ed. 2015, 54, 5399-5403.
2-
bromothymol and 95% (v/v) ethanol). The concentration of SO4 was
determined in triplicate by BaSO4 gravimetric method with 5% (w/v)
BaCl2 as the precipitator. The concentration of borate was determined by
the weight method of mannitol with sodium hydroxide standard solution in
O. Jacquet, C. D. Gomes, M. Ephritikhine, T. Cantat, J. Am. Chem. Soc.
2012,134, 2934-2937.
a) P. Mampuys, H. Neumann, S. Sergeyev, R. V. A. Orru, H. J. Jiao, A.
Spannenberg, B. U. W. Maes, M. Beller, ACS Catal. 2017, 7, 5549-
5556; b) I. Khana, A. Ibrar, W. Ahmed, A. Saee, Eur. J. Med. Chem.
2015, 90, 124-169.
the presence of the double indicator composed of methyl red and
2-
phenolphthalein. The concentration of CO3
was obtained after
neutralization titration and deducting the concentration of borate. The pH
of the brines were determined by a high precision pH meter (PH-7310,
WTW Co., Ltd, Germany) with standard uncertainty ± 0.001.
[9]
T. Mizuno, M. Mihara, T. Nakai, T. Iwai, T. Ito, Synthesis, 2007, 16,
2524-2528.
[10]
[11]
[12]
[13]
[14]
J. Gao, L. N. He, C. X. Miao, S. Chanfreau, Tetrahedron, 2010, 66,
4063-4067.
Catalytic Reaction: As an example, the procedure using 2-
aminobenzonitrile as the substrate was described, and those for other
substrates were similar. In a typical experiment, 2-aminobenzonitrile (2
mmol, 0.2643 g) and brines (3 mL) were loaded into a 22 mL stainless-
steel batch reactor equipped with a magnetic stirrer. The air in the reactor
was removed by blowing CO2 through the reactor. Then desired pressure
of CO2 was charged into the reactor and the reactor was sealed. The
reactor was placed in an oil bath of desired temperature and the reaction
mixture was stirred. After reaction, the reactor was placed in ice water for
15 minutes for cooling, and then the excess CO2 was released slowly.
Afterwards, 25 mL water was added into the reactor, and the mixture was
centrifuged to precipitate the product and the water was removed. Then
the product was washed with tert-butyl methyl ether (3 × 15 mL) and
dried at 95 oC for 3 hours. Finally, the mass of the product was measured
by an electronic balance with an accuracy of 0.0001 g and the isolated
yield was calculated from 2-aminobenzonitriles. The purified products
were characterized by NMR spectrometer. 1H NMR and 13C NMR study
was carried out with a Bruker NMR spectrometer with DMSO-d6 as the
solvent, and the characterization data of the products were seen in
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Keywords: carbon dioxide fixation • basic salt lake brine • mild
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10.1002/cssc.201802431
ChemSusChem
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Entry for the Table of Contents
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Jiayin Hu*, Shangqing Chen,Yafei Guo,
Long Li,Tianlong Deng*
Page No. – Page No.
Basic Salt Lake Brine: Efficient
Catalyst for the Transformation of
CO2 into Quinazoline-2,4(1H,3H)-
diones
Zhabuye basic salt brine was used firstly to efficiently catalyze the reactions of CO2
and 2-aminobenzonitriles to form a series of quinazoline-2,4(1H,3H)-diones under 1
MPa CO2 pressure, and the isolated yields of all desired products are greater than
96%.
This article is protected by copyright. All rights reserved.