Journal of Industrial and Engineering Chemistry 44 (2016) 210215

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Tertiary amines: A new class of highly efcient organocatalysts for CO2

xations
Woolee Choa , Min Seok Shina , Sanggu Hwanga , Hyejin Kima , Min Kima , Jeung Gon Kimb,*
, Youngjo Kima,**
a
Department of Chemistry and BK21+ Program Research Team, Chungbuk National University, Cheongju, Chungbuk 28644, Republic of Korea
b
Department of Chemistry, Chonbuk National University, Jeonju, Jeollabuk-do 54896, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history:
Received 7 August 2016 To realize a true green CO2 utilization process, the development of a catalytic system having no toxic
Received in revised form 20 August 2016 components is essential. Herein, tertiary amines without any metal or halide additives are introduced as
Accepted 2 September 2016 simple and green organocatalysts to activate CO2 and insert into epoxides, producing synthetically
Available online 12 September 2016 important cyclic carbonates. Among those amines, diamine such as N,N,N0 ,N0 -tetraethylethylenediamine
exhibited a moderate to excellent efciency. This new class of organocatalyst which does not have any
Keywords: toxic metals and halides is easy to handle and only requires as low as a 0.1 mol% loading. Additional
Organocatalyst favorable features include solvent free conditions and broad substrate scopes.
tertiary amines
2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Cycloaddition
reserved.
CO2 xation
Epoxide

Introduction
The efcient capture and utilization of carbon dioxide have
been an important theme environmentally and chemically for a
long time [1]. As a main cause of greenhouse effect, CO2 has been
considered as a target to capture and sequestrate [2]. However,
from a synthetic chemistry point of view, CO2 is a valuable
C1 building block, which is nontoxic, non-ammable, inexpensive,
and abundant [3]. Thus, the development of chemical methods to
activate and convert CO2 into valuable products has been a major
eld of research in recent years to mitigate our heavy dependence
on fossil carbon source. In spite of inherent stability and low
activity, many catalytic systems have successfully transformed the
inert CO2 into a variety of chemicals, such as methanol, formic acid,
urea, lactones, cyclic carbonates, and polycarbonates.
Among them, the cyclic carbonates from CO2 and epoxide have
been produced since 1950s and nd their use as polar aprotic
solvents, electrolytes, monomers for polymers, antifoam additives,
and plasticizers [4]. In addition, cyclic carbonates are rapidly
replacing the use of highly toxic phosgene and carbon monoxide in
* Corresponding author. Fax: +82 63 270 3408.
** Corresponding author. Fax: +82 43 267 2279.
E-mail addresses: jeunggonkim@jbnu.ac.kr (J.G. Kim), ykim@chungbuk.ac.kr
(Y. Kim).
organic syntheses [5]. Thus, its research and development have
been a signicant portion on CO2 utilization.
A wide range of catalytic systems has been developed to couple
CO2 and epoxide. Alkali metal salts [6], heterogeneous mineral
oxides [7], transition metal complexes [8], quaternary ammonium
[9] and phosphonium salts [10], and ionic liquids [11] consist of
major classes. Various combinations of two or more catalysts have
also been studied to maximize efciency [12]. However, several
drawbacks still remain to be solved such as the use of toxic and
expensive metal, water and air sensitivity, selectivity, and reactor
corrosion by halides. Therefore, the development of metal- and
halogen-free catalytic systems is in high demand to realize a
greener process. Recently several notable examples of metal- and
halide-free conversion of CO2 into carbonates have emerged,
which utilized combinations of organic base (CO2 activation) and
hydrogen donor (epoxide activation). Binary systems of
DMAP/phenol [13], DBU/cellulose [14], and amino acid/ionic
liquid [15] as well as bifunctional single catalysts such as amino
acid [16] and alkanolamine [17] have been reported. The smart
combination of Lewis base and acid simultaneously activated
epoxide and CO2, resulting desired cyclic carbonates with good
conversion and selectivity. In addition, several single functional
catalysts such as N-heterocyclic carbenes [18], quaternary
ammonium hydroxides [19], dimethyl formamide [20], phospho-
rus ylide CO2 adducts [21], and super-bases [22] recently joined to
the list of metal and halide free CO2 xation catalysts.

http://dx.doi.org/10.1016/j.jiec.2016.09.015
1226-086X/ 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215
Scheme 1. Diamine catalysts for highly reactive CO2 xation into cyclic carbonate.
During our continuous search for highly efcient and environ-
mentally friendly catalytic systems [23], we found one interesting
investigation by Lermontov et al. reported in 1998 [24]. The team
demonstrated that triethylamine itself could catalyze CO2 inser-
tion into epichlorohydrin. In their report, they postulated that
quaternary ammonium salts might be formed in situ from
triethylamine and epichlorohydrin, then catalyzed the carbonate
formation. However, we discovered that simple alkyl amine
catalysts are also effective with other types of epoxides which
would not generate ammonium halide salts. In addition, tertiary
di-amines are found to possess good reactivity under a solvent free
condition (Scheme 1). Given that organocatalytic formation of
cyclic carbonates generally needs high catalyst loading or halide
nucleophiles to obtain a meaningful efciency in general, our
discovery on highly reactive simple amine catalyst would
eliminate those concerns and open a new opportunity for greener
catalytic system development. The details on our ndings are
presented herein.
Scheme 2. Chemical structures of amine compounds in this work and their designations.
211
Experimental
General considerations
All manipulations were performed under an atmosphere of
dinitrogen by using standard Schlenk-type glassware with a dual
manifold Schlenk line. Dinitrogen was deoxygenated using an
activated Cu catalyst and was dried with drierite. All chemicals
including TEA, EDA, MEDA, N,N-DMEDA, N,N0 -DMEDA, TrMEDA,
TMEDA, TEEDA and epoxides were purchased from Aldrich and
used as supplied unless otherwise indicated. Carbon dioxide
(99.999%) was used as received without further purication.
CDCl3 was dried over 4 activated molecular sieves and used
after vacuum transfer to a Schlenk tube equipped with a J. Young
valve.
Measurements
1
H and 13C NMR spectra were recorded at ambient temperature
on a Bruker DPX-400 MHz and 500 MHz NMR spectrometer using
standard parameters. All chemical shifts are reported in d units
with reference to the residual CDCl3 (d 7.24 for 1H NMR; d 77.00 for
13
C NMR).
Synthesis of N,N,N0 ,N0 -tetrahexylethylenediamine (THEDA)
To a stirred solution of sodium hydroxide (0.65 g) in 1.7 mL
distilled water, di-n-hexylamine (18 mmol, 4.2 mL) was slowly
added. 1,2-dibromoethane (7 mmol, 0.6 m L) was then continu-
ously added to the mixture solution. Then, the reaction solution
was heated to 95  C and stirred for 30 hours. The mixture was
cooled to room temperature. The reaction product was separated
from diethyl ether and then washed with distilled water. The
solution was dried with anhydrous MgSO4 and ltered after
stirring for 30 min. The ltrate was concentrated to give crude
212 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215

13
Table 1 C NMR (CDCl3, 125.76 MHz) d 54.8, 52.2, 31.8, 27.3, 27.1, 22.7, 14.0.
Catalyst screening for the cycloaddition reaction of epichlorohydrin and CO2.a HRMS (ESI): calcd. For C26H57N2 [M+H]+ 397.4522; found 397.4516.

Synthesis of N,N,N0 ,N0 -tetrabenzylethylenediamine (TBEDA)

0
To a stirred solution of sodium hydroxide (1.3 g) in 3.3 mL
distilled water, ethylenediamine (18 mmol, 1.2 mL) was slowly
added. Benzyl chloride (55 mmol, 5 m L) was then continuously
added to the mixture solution. Then, the reaction solution was
heated to 95  C and stirred for 4 h. The mixture was cooled to room
Entry Catalyst Conversion (%) TONb TOFc (h1) Selectivityd (%) temperature. The reaction product was separated from diethyl
1 TEA 16 163 47 99 ether and then washed with distilled water. The solution was dried
2e TEA 26 264 75 99 with anhydrous MgSO4, ltered after stirring for 30 min and
3 EDA 0 0 0
4 MEDA 0 0 0
evaporated under vacuum. The desired product TBEDA was
5 N,N0 -DMEDA 0 0 0 obtained as ivory powder in a yield of 14%. 1H NMR (CDCl3,
6 N,N-DMEDA 18 176 50 99 400.13 MHz) d 7.287.18 (m, 20H, Ph-H), 3.50 (s, 8H,  NCH2Ph),
7 TrMEDA 19 194 55 99 2.60 (s, 4H, 
NCH2CH2N ); 13C NMR (CDCl3, 100.61 MHz) d 139.7,
8 TMEDA 23 234 67 99
128.7, 128.1, 126.7, 58.6, 51.1. HRMS (ESI): calcd. For C30H33N2 [M
9 TEEDA 36 364 104 99
10f TEEDA 18 183 52 99 +H]+ 421.2643; found 421.2638.
11 THEDA 32 315 90 99
12 TBEDA 11 110 31 99 Synthesis of N,N,N0 ,N0 -tetraallylethylenediamine (TAEDA)
13 TAEDA 10 95 27 99
a
Reaction conditions: epichlorohydrin = 10 mmol (0.78 mL), [catalyst] = 0.01 To a stirred solution of sodium hydroxide (0.6 g) in 1.7 mL
mmol (0.1 mol%), 100  C, CO2 10 bar, 3.5 h. distilled water, ethylenediamine (9 mmol, 0.6 mL) was slowly
b
Turnover number (TON) = (mol of epichlorohydrin consumed)/(mol of catalyst). added. Allyl chloride (24 mmol, 1.9 m L) was then continuously
c
Turnover frequency (TOF) = TON/reaction time (h).
d added to the mixture solution. Then, the reaction solution was
Calculated by 1H NMR spectral integration.
e
0.2 mol% TEA was used. heated to 95  C and stirred for 36 h. The mixture was cooled to
f
0.05 mol% TEEDA was used. room temperature. The reaction product was separated from
diethyl ether and then washed with distilled water. The solution
was dried with anhydrous MgSO4 and ltered after stirring for
30 min. The ltrate was concentrated to give crude product, which
was puried by distillation under reduced pressure. The desired
product, which was puried by distillation under reduced product TAEDA was obtained as a yellow oil in a yield of 17%. 1H
pressure. The desired product THEDA was obtained as a yellow NMR (CDCl3, 400.13 MHz) d 5.865.76 (m, 4H,  NCH2CHCH2),
oil in a yield of 23%. 1H NMR (CDCl3, 500.13 MHz) d 2.47 (s, 4H, 5.155.07 (m, 8H, NCH2CHCH2), 3.06 (d, J = 6.4 Hz, 8H,
NCH2CH2N ), 2.37 (q, J = 7.5 Hz, 8.7 Hz, 8H, 
NCH2(CH2)4CH3), NCH2CHCH2), 2.52 (s, 4H, NCH2CH2N); 13C NMR (CDCl3,
1.39 (m, 8H, NCH2CH2(CH2)3CH3), 1.30 (m, 24H, 100.61 MHz) d 135.6, 117.3, 57.3, 50.7. HRMS (ESI): calcd. For
NCH2CH2(CH2)3CH3), 0.85 (t, J = 6.8 Hz, 12H,  N(CH2)5CH3); C14H25N2 [M+H]+ 221.2018; found 221.2012.

Table 2
The effect of temperature and pressure on the cycloaddition reaction of epichlorohydrin and CO2 using TEEDA.a

Entry Temp. ( C) CO2 pressure (bar) Conversion (%) TONb TOFc (h1) Selectivityd (%)
1 80 10 13 132 38 99
2 80 20 15 146 42 99
3 80 30 21 212 61 99
4 100 10 36 364 104 99
5 100 20 38 380 109 99
6 100 30 40 403 115 99
7 120 10 59 586 167 99
8 120 20 61 608 174 99
9 120 30 65 645 173 99
10e 120 10 97 967 97 99
a
Reaction conditions: epichlorohydrin = 10 mmol (0.78 mL), [TEEDA] = 0.01 mmol (0.1 mol%), 3.5 h.
b
Turnover number (TON) = (mol of epichlorohydrin consumed)/(mol of catalyst).
c
Turnover frequency (TOF) = TON/reaction time (h).
d
Calculated by 1H NMR spectral integration.
e
Reaction time = 10 h.
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215 213

Table 3
The scope of epoxides on the cycloaddition reaction of epoxide and CO2 using TEEDA.a

Entry Product Time (h) Conv. (%) TONb TOFc (h1) Selectivityd (%)
1 38 86 853 22 99

2 38 58 583 15 99

3 24 12 115 4.8 99

4 10 97 967 97 99

5 12 83 826 69 99

6 39 83 832 21 99

7 42 10 95 2.2 99

8 12 3 33 2.8 99

a
Reaction conditions: epoxide = 10 mmol, [TEEDA] = 0.01 mmol (0.1 mol%), 120  C, CO2 10 bar.
b
Turnover number (TON) = (mol of epichlorohydrin consumed)/(mol of catalyst).
c
Turnover frequency (TOF) = TON/reaction time (h).
d
Calculated by 1H NMR spectral integration.

Representative procedures for the cycloaddition reaction of epoxide
and CO2
The cycloaddition reaction of CO2 to epoxide was carried out
by charging a stirring bar, epoxide (10 mmol), and catalyst
(10 mmol), into a stainless steel pressure reactor (10 mL inner
volume). Then, CO2 was charged in the reactor and the pressure
was adjusted to desired pressure at appropriate temperature. The
reactor was maintained for the desired time. After then, the
pressure reactor was cooled to ambient temperature, and the
excess CO2 was vented. A small sample of mixture was taken for
1
H NMR analysis.
214 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215

Results and discussion

To investigate the effectiveness of a new class of organocatalysts

on the CO2 chemical xation into aliphatic cyclic carbonates,
several amine compounds (Scheme 2) were selected. The amines
explored were triethylamine (TEA), ethylenediamine (EDA),
N-methylethylenediamine (MEDA), N,N0 -dimethylethylenedi-
amine (N,N0 -DMEDA), N,N-dimethylethylenediamine
(N,N-DMEDA), N,N,N0 -trimethylethylenediamine (TrMEDA), N,N,
N0 ,N0 -tetramethylethylenediamine (TMEDA), N,N,N0 ,N0 -tetraethy-
lethylenediamine (TEEDA), N,N,N0 ,N0 -tetrahexylethylenediamine
(THEDA), N,N,N0 ,N0 -tetrabenzylethylenediamine (TBEDA), and N,
N,N0 ,N0 -tetraallylethylenediamine (TAEDA).
The cycloaddition of CO2 to epichlorohydrin (EH) was
performed using various kinds of amine compounds as catalysts
without any other additives including cocatalyst and solvent. We
carried out the reaction at 100  C under a xed [EH]/[catalyst]
molar ratio of 1000, CO2 pressure of 10 bar, and 3.5 h reaction time.
EH was easily converted into the corresponding cyclic carbonate
with high selectivity (>99%). The structural inuence of amines on
the catalytic efciency can be deduced by comparing the data given
in Table 1. As Lermontov and co-workers reported, TEA repeatedly
showed moderate reactivity with epichlorohydrin (Table 1, entry
1). In contrast, primary or secondary amines reveal no catalytic
reaction under the same conditions (entries 35). We next tested a
series of tertiary diamines (entries 612). Under the same reaction
conditions, N,N-DMEDA and TrMEDA with a tertiary monoamine
moiety showed the similar catalytic efciency with TEA (entries
6 and 7). Interestingly, the gradual increase of catalytic activity Scheme 3. Plausible mechanism of tertiary amine catalyzed cycloaddition reaction
along with a number of methyl substituents on nitrogen atoms of CO2 with epoxide.
from N,N-DMEDA was observed (entries 68). Compared with
tertiary monoamine catalysts, tertiary diamines such as TMEDA, (entries 5 and 6). However, substrate with multi-substituents such
TEEDA, and THEDA exhibited the dramatic improvement of as 1,2-epoxy-2-methylpropane (entry 7) and cyclohexene epoxide
catalytic activity (entries 810). Most of tertiary diamine catalysts (entry 8) exhibited low conversions. Table 3 indicates that epoxides
gave good turnover numbers but the introduction of benzyl (entry with short alkyl side (entry 1) chain or heteroatoms (entries 46)
11) and allyl (entry 12) functional groups were not effective. could be easily activated. Among assorted substrates, epichloro-
As catalysts with simple alkyl chains showed excellent hydrin is the most active epoxide for the cycloaddition reaction
efciencies, TEEDA showed best results and was selected for (entry 4). In addition, TEEDA exhibited excellent selectivity
further optimizations (entry 9). The effectiveness of diamine was regardless of epoxide variations. Given that aliphatic polycarbon-
tested as well. When the carbonation reactions were performed at ate and cyclic carbonate formations happen concurrently in many
the same amine functional group concentration of TEA and TEEDA catalytic systems, the exclusive formation of cyclic carbonate is an
at 0.2 mol% (entries 2 and 9) or 0.1 mol% (entries 1 and 10), the interesting feature of this catalyst [8b,25].
performance of diamine catalyst (TEEDA) excelled that of Our results are contrary to the investigation on triethylamine
monoamine (TEA). Diamine structure truly enhanced the catalytic catalyzed CO2 insertion by Lermontov et al. [24], where they
activity over concentration effect. claimed that it worked only with epichlorohydrin not propylene
The selected TEEDA catalyst was optimized with variations of oxide due to in situ formation of quaternary ammonium chloride.
pressure and temperature (Table 2). Turnover numbers increased Simple tertiary amine systems surprisingly displayed high catalytic
by the elevations of both reaction temperature and CO2 pressure; activity with a wide range of epoxides in the absence of
the effect of temperature was more viable. As shown in Table 2, heteroatoms and cocatalysts.
entry 10, at 120  C and 10 bar CO2, the reaction reached almost a Two possible mechanisms for tertiary amine catalyzed cyclo-
completion after 10 h reaction time (TON = 967, theoretical addition reaction are proposed in Scheme 3. Carbamate salt from
TON = 1000). amine and CO2 and quaternary ammonium salt from amine and
With the optimized condition in hands, we next moved to epoxide are key intermediate for Cycles I and II, respectively
investigate the scope of substrates (Table 3). Substrates include [22,26]. A further study on a tertiary amine catalyzed on CO2
various kinds of epoxides such as propylene oxide (entry 1), 1,2- activation and insertion is currently in progress to improve their
epoxybutane (entry 2), 1,2-epoxyhexane (entry 3), epichlorohydrin efciency and scope.
(entry 4), 1,2-epoxy-3-phenoxypropane (entry 5), tert-butyl
glycidyl ether (entry 6), 1,2-epoxy-2-methylpropane (entry 7), Conclusion
and cyclohexene oxide (entry 8). Epoxides with simple alkanes
(R = Me, Et, and n-Bu) showed high dependence on chain length Herein we have described, tertiary amines were introduced as a
(entries 13). While propylene oxide gave an excellent conversion new class of catalyst for CO2 xation into cyclic carbonates. High
(entry 1), a quick loss of reactivity was observed from ethyl to butyl catalytic efciency was obtained using a tertiary diamine catalyst
side chains (entries 2 and 3). Interestingly, when heteroatom was with no assist of additives or cocatalysts. Tertiary amine,
introduced at 3-position, high reactivity was restored. In addition representatively TEEDA herein, exhibited a promise for green
to the model substrate, epichlorohydrin (entry 4), epoxides with catalytic systems by elimination of toxic metals and halogens, low
CH2OPh and CH2OBut substituents gave all excellent TONs catalyst loadings, no need of inert conditions, and solvent free
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215
operations. Further study towards a simple amine catalytic system
having milder reaction conditions are currently in progress.
Acknowledgements
Y.K. thanks the National Research Foundation of Korea (NRF),
the Korean Ministry of Education (MOE) through the Creative
Human Resource Training Project for Regional Innovation (grant
number 2014H1C1A1066874) and Basic Science Research Program
(grant number 2015R1D1A1A01061043) for nancial support. J.G.K
acknowledges the nancial supported by research funds for newly
appointed professors of Chonbuk National University in 2015.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jiec.2016.09.015.
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