pubs.acs.

org/journal/ascecg Research Article

One-Pot Synthesis of N‑Substituted Carbamic Acid Esters from Low

Concentrations of CO2
Hiroki Koizumi, Katsuhiko Takeuchi,* Kazuhiro Matsumoto, Norihisa Fukaya, Kazuhiko Sato,
Masahito Uchida, Seiji Matsumoto, Satoshi Hamura, and Jun-Chul Choi*
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ABSTRACT: Organic syntheses, such as that of N-substituted carbamic acid esters

(CAEs), utilizing low purity and low concentrations of CO2 directly, may help achieve
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two important goalsreducing CO2 emission and producing useful core chemicals
without the energy-consuming processes of purifying and concentrating CO2. Here,
we demonstrate a new synthetic approach for CAEs that uses a combination of two
types of CO2 capture mechanisms, which are constituted by combining an amine and
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and an alcohol and DBU, to form a
protonated DBU carbamate salt and a protonated DBU alkyl carbonate salt,
respectively. This new approach of CAE synthesis can be applied even to the
simulated exhaust gas from fire-power plants, such as 3 vol % of CO2 in N2 or 15 vol %
of CO2 in N2, also containing SO2, NO2, and CO.

KEYWORDS: CCUS, polyurethane raw materials, DBU, titanium alkoxide, simulated exhaust gases

■ INTRODUCTION
Increasing concentration of atmospheric carbon dioxide (CO2)
is one of the main triggers of global warming. Significant
research effort has been devoted toward the technological
development in CO2 capture, utilization, and storage
(CCUS)1−4 to address this urgent problem. In particular,
conversion of CO2 into useful compounds by organic
syntheses is promising from the perspective of reducing CO2
concentration and producing energetically and/or industrially
useful chemicals or their raw materials.5,6 Carbamic acid esters
(CAEs; RNHCOOR′), which can be synthesized from CO2,
are attractive compounds for use as isocyanate stock precursors
of polyurethane, which is widely used for automobile parts,
paint, and fiber.7 A large quantity of CO2 can be utilized and
fixed8 in isocyanate manufacture if the method involving CAE
synthesis from CO2 replaces the present method using
phosgene. An added advantage of this method is that CO2 is
nontoxic and safe compared with toxic phosgene.
The efficient syntheses of CAE from amines and CO2 via
reactions using unsaturated hydrocarbons,9−12 epoxides,13 the
Mitsunobu reagent,14,15 alkyl halides,16,17 and CH2Br2 as a
strong dehydrating agent18 have been previously reported.
However, these reagents are expensive, produce byproducts,
and are not environment-friendly. We recently established a
CAE synthesis method using acetals,19 titanium tetraalkoxides
Ti(OR)420,21 (Figure 1a), or tetra alkyl orthosilicates Si-
(OR)422−24 as renewable and reusable reagents. Tomishige et
al. and Meng et al. have independently reported environment-
friendly syntheses of CAE from CO2 using CeO2 catalysts.25,26
These reactions all use high-purity and high-quality CO2, and
most, especially the environment-friendly ones, also require
high-pressure CO2. However, the concentration of CO2 in the
exhaust gases from thermal power plants, which are desired for
use as a CO2 source to reduce CO2 emissions, is reported to be
approximately 3−20%.27−29 It is necessary to concentrate,
compress, and purify CO2 in these exhaust gases, at high
expense and consuming large amounts of energy, before use in
the aforementioned CAE synthesis methods. The efficacy of
the process for concentrating, compressing, and purifying CO2
in these exhaust gases has improved due to advancements in
chemical process engineering and other technologies.30−35
However, the most energy-efficient method is the direct use of
low purity and low concentrations of CO2.
To convert low concentrations of CO2 into useful chemicals
for utilization, it is essential to elucidate the mechanism of
collecting and concentrating CO2 in reaction systems using
appropriate CO2 absorbents. However, there are very few
reports that focus on applying the mechanism for CO2 capture
from low concentrations of CO2, such as atmospheric CO2 or
Received: January 5, 2022
Revised: March 31, 2022
Published: April 15, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acssuschemeng.2c00095

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Figure 1. CO2 capture methods and synthesis of CAEs. (a) Our previous work on CAE synthesis. (b) CO2 capture of amine and DBU to produce
[DBUH][RNHCOO] and CO2 capture of alcohol and DBU to produce [DBUH][R′OCOO]. (c) Strategy of efficient CAE synthesis from low
concentrations of CO2 applying the combined use of the two CO2 capture systems and Ti(OR)4 as a regenerable alkoxide source and dehydrating
agent.
exhaust gases for CO2 transformation. Yoshida et al. reported
the synthesis of oxazolidinones from propargylic amines with
1,6-diazabicyclo[5,4,0]undec-7-ene (DBU) under air bub-
bling.36,37 Parkash et al. and Beller et al. reported the
hydrogenation of CO2 captured from air to methanol or
formates using carbamates or bicarbonates synthesized from
polyamines, amino acids, or hydroxides with ruthenium
catalysts.38−41 We also accomplished the synthesis of urea
derivatives utilizing alkyl ammonium carbamates derived from
alkyl amines and gases containing CO2 at low concentrations,
including air or simulated exhaust gas, with a titanium
catalyst.42 In these reactions, dilute CO2 is concentrated by
chemisorption using bases as substrates and/or absorbents.
The synthesis of CAEs, for which high-purity CO2 is essential,
can also be achieved by incorporating an appropriate CO2
capture mechanism from low concentrations of CO2. In this
article, we present a CAE synthesis method to optimize the use
of low-concentration and low-purity CO2 sources such as
exhausted gas including some impurities (i.e., SOx and NOx)
from coal-fired power plants, combining two CO2 capture
methods based on chemisorption: formation of alkyl or aryl
carbamate protonated DBU cation salt ([DBUH]-
[RNHCOO])43−45 and alkyl carbonate protonated DBU
cation salt ([DBUH][R′OCOO])46−48 (Figure 1b). This
method can be operated as a one-pot system by integrating
from CO2 capture to conversion to CAEs with titanium
alkoxide, which can be regenerated from reaction residue
Ti(OR)n(OH)n−4 by alcohol or dialkylcarbonate (Figure 1c).
■ RESULTS AND DISCUSSION
CO2 Capture Using [DBUH][RNHCOO] and [DBUH]-
[R′OCOO] Formed from Amines, Alcohols, and DBU.
First, the formation of [DBUH][RNHCOO] and [DBUH]-
[R′OCOO] was examined at low concentrations of CO2
because these salt formations have never been reported using
CO2 at low concentrations. When n-hexylamine (n-HexNH2)
(as a model substrate for aliphatic amines) and DBU were
bubbled in N-methyl-2-pyrrolidone (NMP) by 15 vol % CO2
(CO2/N2 = 15:85, v/v) equivalent to coal-fired power plant
exhaust gas, the 1H NMR signals attributed to DBU shifted to
the position reported for the equilibrium mixture of DBU and
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DBUH+48,49 and the signal assignable to the α -protons of n-
HexNH2 (δ 2.56 ppm) also disappeared from the 1H NMR
spectrum of the reaction mixture after bubbling (Figure 2a).
Therefore, we estimated that [DBUH][n-HexNHCOO] was
obtained quantitatively, which was supported by the fact that
2.0 mmol of CO2 was captured in this system, as mentioned
later. Since two triplet signals of α-protons were observed at
2.94 and 3.56 ppm after bubbling and the sum of the integral
intensity ratio of these signals was 2:3 to the integral intensity
ratio of the terminal CH3 signal of the n-hexyl group at 0.86
ppm, and two signals attributed to captured CO2 also appeared
at 157.5 and 161.8 ppm in the 13C NMR spectrum (see
Supporting Information Figure S2), we assumed that two
conformational isomers of n-HexNHCOO− derived from
amido moiety had formed. To confirm the formation of
[DBUH][n-HexNHCOO], FT-IR spectroscopy and ESI-MS
were performed. FT-IR spectra of NMP solutions of n-
HexNH2 and DBU after bubbling of 15 vol % CO2 showed a
new absorption band at 1645 cm−1, which is consistent with
previously reported carbonyl vibrations of carbamate species.50
In addition, the mass spectrum (HRMS-ESI) of this reaction
mixture showed signals assignable to n-HexNHCOO− (m/z
calcd for C7H14NO2: 144.1019; found 144.0989) and DBUH+
(m/z calcd for C9H17N2: 153.1386; found 153.1405),
respectively. Similar experiments were conducted using 6.5
mmol of n-BuOH instead of n-HexNH2. [DBUH][n-
BuOCOO] was obtained in 58% yield from DBU, determined
from the independent signal of the α-proton in n-BuOCOO−
at 3.73 ppm (Figure 2b). The formation of [DBUH][n-
BuOCOO] was determined by FT-IR (1670 and 1628 cm−1)
and HRMS-ESI (m/z calcd for C5H9O3: 117.0546; found
117.0522). Using both 2.0 mmol of n-HexNH2 and 6.5 mmol
of n-BuOH, 2.0 mmol and 2.6 mmol of [DBUH][n-
HexNHCOO] and [DBUH][n-BuOCOO] were formed,
respectively (see Supporting Information Figures S5 and S6).
When using 2.0 mmol of aniline (PhNH2) (as a model
substrate of an aryl amine) instead of n-HexNH2, [DBUH]-
[PhNHCOO] was formed quantitatively (see Supporting
Information Figures S7 and S8). The formation of [DBUH]-
[PhNHCOO] was determined by NMR, FT-IR (1645 cm−1),
and HRMS-ESI (m/z calcd for C7H6NO2: 136.0393; found:
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Figure 2. 1H NMR spectra to determine the formation of [DBUH][n-
HexNHCOO] (a) and [DBUH][n-BuOCOO] (b). Two millimole of
n-HexNH2 or 6.5 mmol of n-BuOH with 6.0 mmol of DBU, 0.1 mL of
DMSO-d6, and 1,3,5-trimethylbenzene (mesitylene) as an internal
standard were dissolved in 0.5 mL of NMP, and then 15 vol % CO2
was bubbled (0.1 L/min) for 20 min at room temperature. These
spectra were measured in DMSO-d6 before/after bubbling. Black
down-pointing triangle: NMP, black club suit: mesitylene, single
dagger: DBU, double dagger: equilibrium mixture of DBU and
[DBUH]+, black square: n-HexNH2, white square: n-HexNHCOO−,
black diamond: n-BuOH, and white diamond: n-BuOCOO−.
136.0353). These results clearly show that alkyl and aryl
[DBUH][RNHCOO] and [DBUH][R′OCOO] salts can be
obtained from low concentrations of CO2, e.g., 15 vol % CO2.
To understand the efficiency of CO2 capture using amines,
alcohols, and DBU, the quantity of CO2 contained in the outlet
gas during bubbling was monitored by gas chromatography
(GC) analysis (see Supporting Information Figures S9 and
S10). Then, the total captured CO2 was mathematically
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estimated from the measured outlet CO2 quantities and
plotted against time and compared to the estimated total
bubbled quantity of CO2 (Figure 3). When the NMP solution
of n-HexNH2 and DBU was used, almost all of the bubbled
CO2 was captured up to about 3 min, after which the capture
efficiency gradually decreased (Figure 3a). The quantity of
captured CO2 did not increase after about 5 min. The total
captured quantity of CO2 was approximately 2 mmol,
consistent with the theoretical quantity of captured CO2 if
all of the n-HexNH2 and DBU were converted to [DBUH][n-
HexNHCOO]. When the NMP solution of n-BuOH and DBU
was used, the total captured CO2 was clearly less than the total
bubbled quantity of CO2 after about 2 min, while the quantity
of captured CO2 continued to increase gradually and reached
3.2 mmol after about 13 min (Figure 3b). Theoretically, 6
mmol of CO2 should be captured as maximum based on the
quantity of n-BuOH and DBU used. Therefore, alcohols are
less reactive with CO2 because their nucleophilicity is lower
than that of amines, and it is assumed that the capture of CO2
by n-BuOH and DBU competes with the release of CO2 from
[DBUH][n-BuOCOO], during the 15 vol % CO2 bubbling, to
induce an equilibrium. When using both n-HexNH2 and n-
BuOH, together with DBU as an NMP solution, a larger
amount of CO2 could be captured faster than when n-HexNH2
or n-BuOH was used alone (Figure 3c). The total captured
quantity of CO2 was 4.3 mmol at about 13 min, which was
almost similar to the estimated quantity (from NMR) of
[DBUH][n-HexNHCOO] and [DBUH][n-BuOCOO] men-
tioned above. When using PhNH2 with DBU, the total
quantity of CO2 captured reached the theoretical value (2
mmol), while the CO2 capture rate was comparatively slower
than that of n-HexNH2 with DBU (see Supporting Information
Figure S11). Thus, the combination of amines, n-BuOH, and
DBU can efficiently capture CO2 from low-concentration CO2.
However, in our previous study on the synthesis of CAE from
high-pressure CO2 using regenerable metal alkoxides, we
reported that an excess of protic solvents, such as alcohols,
inhibits CAE synthesis.21 In other words, the addition of n-
BuOH has the following paradoxes in CAE synthesis: (1) n-
BuOH promotes the reaction by capturing CO2 together with
DBU as [DBUH][n-BuOCOO] and (2) n-BuOH inhibits the
reaction as a protic solvent. Based on the above, we concluded
that the quantities of amines, n-BuOH, and DBU should be
optimized by examining the actual CAE synthesis using the
captured CO2.
One-Pot CAE Synthesis Using [DBUH][RNHCOO] and
[DBUH][R′OCOO]. Next, we investigated the development of
a one-pot reaction to convert CO2 captured from low-
concentration CO2 gas directly to CAEs using Ti(OR)4. It is
known that scrambling of alkoxy groups occurs between
Ti(OR)4 and alcohols; therefore, the alkyl chains of each
should be matched. In addition, the saturated steam pressure
of the alcohol should be high to avoid alcohol volatilization
during bubbling. Thus, we selected a combination of Ti(On-
Bu)4 and n-BuOH as the first choice for the synthesis of CAE
(see Supporting Information Table S1 for shorter alkyl chain
combinations). First, we investigated the solvents used in the
synthesis of CAE 1a by the reaction of Ti(On-Bu)4 with
[DBUH][n-HexNHCOO] and [DBUH][n-BuOCOO] gen-
erated in situ from n-HexNH2, DBU, and 15 vol % CO2 (Table
1). Using n-BuOH as a single component solvent, 1a was
obtained in only 33% yield with by-production of N,N′-
dihexylurea 2 in 11% yield (entry 1). When the synthesis of 1a
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Figure 3. Estimation of captured CO2 quantity under several conditions. 15 vol % CO2 was bubbled at 0.1 L/min at room temperature. Total
quantities of captured CO2 were calculated from the GC analysis of the outlet gas during bubbling. The capturable maximum quantity means the
sum of the maximum quantity of [DBUH][n-HexNHCOO] and/or [DBUH][n-BuOCOO] that can be produced under each condition. (a) n-
HexNH2 (2.0 mmol), DBU (6.0 mmol), and NMP (0.5 mL). (b) n-BuOH (6.5 mmol), DBU (6.0 mmol), and NMP (0.5 mL). (c) n-HexNH2 (2.0
mmol), n-BuOH (6.5 mmol), DBU (6.0 mmol), and NMP (0.5 mL).

Table 1. Investigation of Additional Solvent for CAE 1a Synthesis

NMR yield (%)

entry additional solvent 1a 2
1 n-BuOH 33 11
2 NMP 90 2
3 1,3-dimethyl-2-imidazolidone 83 2
4 MeCN 74 3
5 THF 61 8
6 1,4-dioxane 73 6
7 o-dichlorobenzene 67 6

Table 2. Investigation of Appropriate Organic Bases

NMR yield (%)

entry organic base pKa in MeCN51,52 1a 2
1 1,8-bis(dimethylamino)naphthalene(proton sponge) 18.62 36 20
2 N,N-diisopropylethylamine (Hunig base) 18.8a 45 22
3 1,1,3,3-tetramethylguanidine (TMG) 23.3 10 0
4 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) 23.89 70 3
5 DBU 24.33 90 2
6 7-methyl-1,5,7-triazabicyclo[4.4.0]-dec-5-ene (MTBD) 25.44 78 6
7 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD) 25.98 0 7
a
This is estimated value, which is probably almost equal to the pKa value of triethylamine in MeCN.

was conducted without Ti(On-Bu)4, 1a almost did not form;
thus, Ti(On-Bu)4 was necessary for this CAE synthesis. As a
result, we succeeded in synthesizing CAE from low
concentrations of CO2; however, the yield might be lowered
due to the presence of excessive amounts of alcohol, as was
feared. Thus, the reaction with some solvents in addition to n-
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BuOH was performed (entries 2−8). As additional solvents,
nonprotic polar solvents were selected because these are
effective for CAE synthesis using high-pressure CO2 and
titanium alkoxides in previous our studies19,20 and were
expected to prevent precipitation of [DBUH][RNHCOO] and
[DBUH][R′OCOO] during bubbling. Solvents that thermally
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Figure 4. Time course of the yield of 1a (a) and 3a (b) at several reaction temperatures. Bubbling conditions: n-HexNH2 (2.0 mmol) or PhNH2
(2.0 mmol), DBU (6 mmol), and n-BuOH (0.6 mL) in NMP (0.5 mL) were bubbled with 15 vol % CO2 for 20 min (0.1 L/min). Reaction
conditions: Ti(On-Bu)4 (2.0 mmol) and NMP (2.5 mL) were added after bubbling. The mixed solution was heated in a 6 mL sealed reaction
vessel. Typically, 180 °C: red circle and line, 150 °C: orange triangle and line, 140 °C: green square and line, 130 °C: blue diamond and line, and
120 °C: purple circle and dotted line.
decompose at high reaction temperatures, such as DMF, DMA,
and DMSO, were excluded. No matter which mixture of
solvents was used, the 1a yield was dramatically improved as
compared to n-BuOH (61−90%, entries 2−8). Especially,
when n-BuOH was mixed with N-methyl-2-pyrollidone
(NMP), a high yield was obtained at 90% (entry 2).
We also experimented with several mixing ratios between n-
BuOH and NMP to optimize the quantity of each solvent (see
Supporting Information Figure S12). The initial reaction rate
increased with the decreasing mixing ratio of n-BuOH.
However, when only NMP was used as the solvent, the
maximum yield was 80%, which was lower than that of the
mixed solvent (n-BuOH/NMP = 0.6:3.0 mL), and the yield
decreased as the reaction was prolonged. In other words,
although an excessive amount of n-BuOH inhibits the reaction
progress, the use of mixed solvents with an appropriate
quantity of n-BuOH is effective for stabilizing the CAE and
improving its yield and that of the CO2 captured.
Then, several organic bases were tested for efficient CAE
synthesis from low concentrations of CO2. The results of the
reactions in the order of basicity (pKa of the conjugated acid)
of the bases are shown in Table 2,51,52 entries 1−8. Although
most of the bases gave 1a in moderate to high yields (entries 1,
2, and 4−8, 36−90%), the reaction hardly proceeded when
TMD or TBD was used (entries 3 and 7). Since TMG and
TBD have an N−H moiety that is reactive with CO2 and is
more basic than hexylamine, it is assumed that they react with
CO2 preferentially over hexylamine and 1a was hardly
obtained. Interestingly, for bases without N−H moiety, the
yield of 1a tended to increase with increasing basicity in the
range from the proton sponge to DBU (entries 1, 2, 4, and 5),
while the yields tended to decrease for MTBD with higher
basicity than DBU (entries 6 and 8). To assume the reason
why the yield decreased in pKa of DBU as a top, the captured
quantities of CO2 were estimated under the similar bubbling
conditions to the reaction described in Supporting Information
Figure S11. Using a proton sponge and Hunig base with much
lower basicity than DBU gave a much smaller captured
quantity of CO2 about 1.0 mmol than that of DBU (see
Supporting Information Figure S13, red and blue line,
respectively). Therefore, the low yields of 1a in the use of
these bases were clearly coursed by the smaller captured
quantities of CO2. In the case of using DBN, although CO2
capture efficiency was slightly lower than DBU, since the total
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captured quantity of CO2 was 4.1 mmol at 20 min and almost
consisted with the use of DBU at 20 min bubbling, it is
assumed that captured CO2 quantity hardly affected to the
yield of 1a. From this result, DBN probably influences the
deprotonation process from amine or alcohol, as shown in step
3 of the proposed reaction mechanism in Figure 5. On the
other hand, the decrease in yield when using MTBD, which is
more basic than DBU and captured much higher quantity of
CO2 (5.1 mmol) than DBU, is thought to be due to the
unfavorable proton-donation process from onium coursed by
strong basicity, which is shown in the explanation of the
presumed reaction mechanism step 3 in Figure 5.
From these results, we concluded that DBU is the best base
for the CAE synthesis from low concentrations of CO2. Then,
DBU quantity was examined in a range of 2−8 mmol, as shown
in Supporting Information Figure S14. The formation rate of
1a increased up to 6 mmol of DBU, after which no significant
difference was observed. Thus, more than 6 mmol of DBU was
necessary to obtain a sufficient reaction rate.
To investigate the optimal reaction temperature, the time
course of the yield of 1a was measured at several reaction
temperatures (Figure 4a). Although the yield of 1a reached
90% at 180 °C at 3 h, 1a gradually decomposed when the
reaction time was longer than 3 h. In contrast, the
decomposition of 1a was not clearly observed at temperatures
below 150 °C, and the yield of 1a reached 90% after 5 h at 150
°C and after 15 h at 140 °C, respectively. In addition, even
though the substrates, namely, n-HexNH2 and Ti(On-Bu)4,
remained in the reaction mixture, the yields were maintained at
approximately 90% even with longer reaction times at 140 and
150 °C. These results suggested that the reaction reached
equilibrium. At 150 °C, the maximum inner pressure of the
reaction vessel was 1.03 MPa (see Supporting Information
Figure S15). We also measured a similar time course for the
synthesis of N-phenylcarbamic acid n-butyl ester, 3a, using
PhNH2 instead of n-HexNH2, to investigate the difference in
reactivity between aliphatic amines and aromatic amines
(Figure 4b). At 180 °C, 3a formed was much more notably
decomposed than 1a. The decomposition of 3a almost
eliminated at below 150 °C except for a long-time reaction
for 25 h at 150 °C. Although the formation rate of 3a shows a
trend similar to that of 1a, the upper limit of the yield is
approximately 70%, which appears to be the equilibrium yield.
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Table 3. Influence of CO2 Capture Methods and Reagents for 1a Synthesis

reagentsa NMR yield (%)

b
entry n-HexNH2/2.0 mmol n-BuOH/6.5 mmol DBU/6.0 mmol Ti(On-Bu)4/2.0 mmol NMP /total 3.0 mL 1a 2
1 ● ● ● ○ ● (0.5 mL) 86 3
2 ○ ○ ○ ○ ● (3.0 mL) 0 3
3 ● ○ ○ ○ ● (0.5 mL) 13 32
4 ○ ● ○ ○ ● (3.0 mL) 0 4
5 ○ ○ ● ○ ● (1.5 mL) 0 12
6 ● ○ ● ○ ● (0.5 mL) 61 9
7 ○ ● ● ○ ● (0.5 mL) 75 3
8 ● ● ● ● ● (0.5 mL) 84 6
a
Reagents marked with a closed circle were used during bubbling, and reagents marked with an open circle were added after bubbling. bThe
quantity of NMP in parentheses was used during bubbling. After bubbling, NMP was added to bring the total quantity of NMP to 3 mL.

Figure 5. Proposed reaction mechanism.

In this case, the quantity of CO2 captured during 15 vol %
CO2 bubbling was 4.0 mmol (see Supporting Information
Figure S11) and was not significantly different from that
obtained using n-HexNH2 (4.3 mmol). This result suggests
that the equilibrium in the synthesis of 3a is more biased
toward the primitive system than that of 1a. These equilibrium
limitations observed in the syntheses of 1a and 3a are
discussed in detail later.
Under optimized condition, a control experiment on the
synthesis of 1a was conducted (Table 3). The reagents were
added either before or after bubbling 15 vol % CO2 to
investigate the factors governing the synthesis of CAEs from
low concentrations of CO2. We afford 1a and urea derivative 2
in 86 and 3% yields, respectively (entry 1). When only n-
HexNH2 and NMP were present during bubbling 15 vol %
CO2, only a small quantity of 1a (13%) and the moderate
quantity of 2 (32%) were obtained (entry 3). As previously
reported in our study on the synthesis of urea derivatives from
low concentrations of CO2, n-HexNH2 can react with low
concentrations of CO2 on its own to form ammonium
carbamate salts [n-HexNH3][n-HexNHCOO], which can
capture half the moles of CO2 of used n-HexNH2. Therefore,
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carbamate ester could have been obtained even with CO2
capture using only n-HexNH2. However, since the molar
quantity of CO2 is only half that of n-HexNH2 and the
equivalent of CO2 is absolutely insufficient for the synthesis of
1a, the yield of 1a would be lower, and the urea derivative 2
formed by the 2:1 reaction of n-HexNH2 and CO2 would be
preferentially produced. In our previous report on the synthesis
of CAE from high-pressure CO2, we also found that the by-
production of urea derivatives tended to increase as the
quantity of CO2 decreased.21 By bubbling to only n-BuOH or
DBU in NMP, 1a was not obtained at all because n-BuOH or
DBU alone can hardly capture CO2 (entries 4 and 5). When n-
HexNH2 or n-BuOH was presented with DBU in an NMP
solution during bubbling, which produces [DBUH][n-
HexNHCOO] or [DBUH][n-BuOCOO], the yields of 1a
were 61 and 75%, respectively (entries 6 and 7). However,
these yields were lower than the yield in the case of the
coexistence of n-HexNH2, n-BuOH, and DBU shown in entry
1 (86%). Since the quantity of captured CO2 was highest (4.3
mmol) at entry 1, followed by entry 7 (3.2 mmol) and entry 6
(2.0 mmol), as shown in Figure 3, this quantity was reflected in
the yield of 1a. In the case of the presence of all of the reagents
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Figure 6. Substrate scope of CAE synthesis. Isolated yields are described in parenthesis. Bubbling conditions: monoamine (2.0 mmol) or diamine
(1.0 mmol), DBU (6.0 mmol), and n-BuOH (0.6 mL) in NMP (0.5 mL) were bubbled with 15 vol % CO2 for 20 min (0.1 L/min). Reaction
conditions: Ti(On-Bu)4 (2.0 mmol) and NMP (2.5 mL) were added after bubbling, and the mixed solution was heated in a 6 mL sealed reaction
vessel at 150 °C for 5 h. Yields were determined from 1H NMR using mesitylene as an internal standard. (a) 3 vol % CO2 was bubbled at 0.12 L/
min of flow rate for 1 h. (b) Simulated exhaust gas (CO2: 15 vol %, CO: 300 ppm, SO2: 500 ppm, NO2: 500 ppm, N2: balance) was bubbled (0.10
L/min) for 20 min. (c) Reaction time was 7 h.

and solvents during 15 vol % CO2 bubbling, the yield of 1a was
84% and almost similar to entry 1 (entry 8). These results
indicate that the presence of the three components, amines, n-
BuOH, and DBU, during CO2 bubbling is necessary to obtain
CAEs from low concentrations of CO2 in high yields.
The proposed reaction mechanism, based on the above-
mentioned experimental results and our previous reports on
CAE synthesis using high-pressure CO2 and Ti(OR)4, for the
synthesis of CAE using low concentrations of CO2 and Ti(On-
Bu)4, is shown in Figure 5. In step 1, the captured CO2 is
released from [DBUH][RNHCOO] and [DBUH][n-BuO-
COO], as reported53 by heating. In step 2, the released CO2
inserts into the Ti−O bond of Ti(On-Bu)4 to form the
carbonate complex Ti(On-Bu)4‑n(OC(O)On-Bu)n.20,21,54
Since [DBUH][RNHCOO] formed from alkyl amines is
relatively stable at high temperatures (see Supporting
Information Figure S16), a pathway in which the carbamate
anion (RNHCOO−) reacts directly with Ti(On-Bu)4 to give
the carbamate complex Ti(On-Bu)4‑n(OC(O)ONHR)n is also
possible. However, because [DBUH][n-BuOCOO] readily
decomposes and releases CO2 at high temperature as
reported,48 the ligand substitution between n-BuOCOO− and
Ti(On-Bu)4 is assumed to be almost nonexistent. In step 3, the
nucleophilic attack of the amine on Ti(On-Bu)4‑n(OC(O)On-
Bu)n and of n-BuOH on Ti(On-Bu)4‑n(OCONHR)n results in
the formation of CAE and titanium hydroxide Ti(On-
Bu)4‑n(OH)n. In this step, Ti(IV) activated carbonyl carbon
of alkyl carbonate or carbamate ligands for this nucleophilic
attack with its Lewis acidity. Relatively basic solvents like NMP
would assist in the proton transfer at the nucleophilic attack of
5513
amines and alcohols, thus accelerating the reaction. In
addition, we confirmed that the reaction rate increased with
increasing DBU content (see Supporting Information Figure
S17). After the base accepts a proton in step 3, the proton
needs to be donated to form titanium hydroxide, and this
process is inhibited when the base is too strong. In our new
CAE synthesis from low concentrations of CO2, the yield of
CAE appeared to be limited by the equilibrium, which depends
on the reactivity of the amines and the quantity of captured
CO2. Indeed, we experimentally confirmed the reverse
reactions of CAE with water, which was obtained from
Ti(On-Bu)4‑n(OH)n and n-BuOH to produce the amine, n-
BuOH, and CO2 (reverse reaction in Figure 5, see Supporting
Information Figure S18).
Based on the results of the preceding experiments, the
substrate scope with the optimal reaction conditions was
examined (Figure 6). First of all, 1a was obtained in 90% yield
(80% isolated yield) under the optimal reaction conditions.
This isolation yield is comparable to our previously reported
isolation yield (82%) in a similar reaction using high-pressure
pure CO2 and Ti(On-Bu)4.20 In addition, the yield of 1a was
successfully obtained at 75% on 20 times larger scale, in which
40 mmol of n-HexNH2, 120 mmol of DBU, 40 mmol of
Ti(On-Bu)4, 12 mL of n-BuOH, and 60 mL of NMP were used
than standard reaction condition. This result indicated the
possibility of further scale-up. When a series of other aliphatic
amines were used, benzylamine and cyclohexylamine gave
corresponding CAEs 1b and 1c in high isolated yields (77 and
81%, respectively), while the relatively bulky t-butylamine
afforded 1d in low isolated yield (34%). The optimal reaction
https://doi.org/10.1021/acssuschemeng.2c00095
ACS Sustainable Chem. Eng. 2022, 10, 5507−5516
ACS Sustainable Chemistry & Engineering
conditions were also suitable for the synthesis of N-aromatic
CAEs, and 3a was obtained from aniline in 64% isolated yield.
Aniline derivatives with an electron-donating substituent (Me
or MeO group) at para-position gave higher isolated yields of
corresponding CAEs 3b and 3c than aniline (69 and 74%,
respectively). On the other hand, for the 3c isomers, 3d and 3f,
which have a MeO group in the meta- and ortho-positions,
respectively, the isolation yields tended to decrease with
increasing steric hindrance (61% for 3d and 43% for 3f,
respectively). When aniline derivatives with electron-with-
drawing bromo and nitro groups attached to the para-position
were used, the yields of corresponding CAEs 3g and 3h were
decreased (51% isolated yield and 14% NMR yield,
respectively). We also investigated the synthesis of bis-CAEs
(4a−4c), which are precursors of industrially important
isocyanates (hexamethylene diisocyanate (HDI), methylenedi-
phenyl diisocyanate (MDI), and toluene diisocyanate (TDI))
from the corresponding diamines. As a result, N-aliphatic bis-
CAE 4a, which can be converted into HDI, was obtained from
1,6-hexyldiamine in 80% yield. N-Aryl bis-CAE 4b, which can
be converted into MDI, a polyurethane raw material, was also
successfully synthesized in 58% isolated yield. Although it was
also possible to synthesize 3c, which could be converted to
TDI, the isolation yield was only 32%. We also demonstrated
CAE synthesis from two types of simulated exhaust gases: a
lower concentration of 3 vol % CO2 gas simulating LNG-fired
power plant exhaust gas (CO2: 3 vol %, N2: 97 vol %)29 and a
15 vol % CO2 gas with impurities simulating coal-fired power
plant exhaust gas (CO2: 15 vol %, CO: 300 ppm, NO2: 500
ppm, SO2: 500 ppm, N2: balance).28 Even when 3 vol % CO2
was used for bubbling, 1a and 3a were obtained in 78 and 59%
yields, respectively (Figure 6, red text). When simulated
exhaust gas of coal-fired power plant was used for the synthesis
of 1a and 3a, their NMR yields were approximately the same as
those obtained using 15 vol % CO2 (Figure 6, blue text). In
our method, CO2 was captured from the simulated exhaust gas
under ambient temperature and pressure, and thus, the
reaction of substrates with impurities such as SO2 and NO2
would be prevented. In addition, these impurities would go
through from the reaction solution during bubbling. As this
result, the CAE synthesis was considered to proceed even
when using simulated exhaust gas containing some impurities.
Therefore, our method could be applied to the synthesis of
aliphatic and aryl CAEs, including industrially important
compounds from 15 vol % CO2 and simulated exhaust gas
containing impurities.
■
CONCLUSIONS
We demonstrated the one-pot synthesis of CAEs using various
amines and regenerable Ti(On-Bu)4 from low concentrations
of CO2 by combining two CO2 capture methods, which
utilized the formation of [DBUH][RNHCOO] and [DBUH]-
[R′OCOO]. We also found that DBU and n-BuOH contribute
to the capture of CO2 and to the efficiency of the formation of
CAEs. In addition, we have succeeded in synthesizing bis-
CAEs from diamines, which are the raw materials for
polyurethane. We also achieved the synthesis of CAEs from
the simulated exhaust gases of coal-fired and LNG-fired power
plants, in yields comparable to that obtained using simple 15
vol % CO2. Therefore, only CO2 contained in exhaust gases,
amines, and alcohols is consumed, and only water is produced
in this reaction. We believe that this CAE synthesis method is
an innovative approach that combines both energy efficiency
5514
pubs.acs.org/journal/ascecg Research Article
and environmental compatibility, allowing the simultaneous
reduction of CO2 emissions and the production of industrially
valuable compounds.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00095.
General information, experimental procedures, and
additional results were described (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Katsuhiko Takeuchi − National Institute of Advanced
Industrial Science and Technology (AIST), Tsukuba Central
5, Tsukuba 305-8565 Ibaraki, Japan; orcid.org/0000-
0002-2720-5394; Email: takeuchi-k@aist.go.jp
Jun-Chul Choi − National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba Central 5,
Tsukuba 305-8565 Ibaraki, Japan; orcid.org/0000-
0002-7049-5032; Email: junchul.choi@aist.go.jp
Authors
Hiroki Koizumi − National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba Central 5,
Tsukuba 305-8565 Ibaraki, Japan
Kazuhiro Matsumoto − National Institute of Advanced
Industrial Science and Technology (AIST), Tsukuba Central
5, Tsukuba 305-8565 Ibaraki, Japan; orcid.org/0000-
0003-1580-8822
Norihisa Fukaya − National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba Central 5,
Tsukuba 305-8565 Ibaraki, Japan; orcid.org/0000-
0001-8319-803X
Kazuhiko Sato − National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba Central 5,
Tsukuba 305-8565 Ibaraki, Japan; orcid.org/0000-
0002-4929-4973
Masahito Uchida − Advanced Materials Research Laboratory,
Tosoh Corporation, Kanagawa 252-1123, Japan
Seiji Matsumoto − Advanced Materials Research Laboratory,
Tosoh Corporation, Kanagawa 252-1123, Japan
Satoshi Hamura − Tosoh Corporation, Tokyo 105-8623,
Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.2c00095
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank Yusuke Kurokawa for his assistance with the
experiment. This work was supported by “Uncharted Territory
Challenge 2050 (Mitou challenge 2050)” (K.T.) from New
Energy and Industrial Technology Development Organization
(NEDO).
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