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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 organic syntheses [5]. Thus, its research and development have
been a signicant portion on CO2 utilization.
The efcient capture and utilization of carbon dioxide have A wide range of catalytic systems has been developed to couple
been an important theme environmentally and chemically for a CO2 and epoxide. Alkali metal salts [6], heterogeneous mineral
long time [1]. As a main cause of greenhouse effect, CO2 has been oxides [7], transition metal complexes [8], quaternary ammonium
considered as a target to capture and sequestrate [2]. However, [9] and phosphonium salts [10], and ionic liquids [11] consist of
from a synthetic chemistry point of view, CO2 is a valuable major classes. Various combinations of two or more catalysts have
C1 building block, which is nontoxic, non-ammable, inexpensive, also been studied to maximize efciency [12]. However, several
and abundant [3]. Thus, the development of chemical methods to drawbacks still remain to be solved such as the use of toxic and
activate and convert CO2 into valuable products has been a major expensive metal, water and air sensitivity, selectivity, and reactor
eld of research in recent years to mitigate our heavy dependence corrosion by halides. Therefore, the development of metal- and
on fossil carbon source. In spite of inherent stability and low halogen-free catalytic systems is in high demand to realize a
activity, many catalytic systems have successfully transformed the greener process. Recently several notable examples of metal- and
inert CO2 into a variety of chemicals, such as methanol, formic acid, halide-free conversion of CO2 into carbonates have emerged,
urea, lactones, cyclic carbonates, and polycarbonates. which utilized combinations of organic base (CO2 activation) and
Among them, the cyclic carbonates from CO2 and epoxide have hydrogen donor (epoxide activation). Binary systems of
been produced since 1950s and nd their use as polar aprotic DMAP/phenol [13], DBU/cellulose [14], and amino acid/ionic
solvents, electrolytes, monomers for polymers, antifoam additives, liquid [15] as well as bifunctional single catalysts such as amino
and plasticizers [4]. In addition, cyclic carbonates are rapidly acid [16] and alkanolamine [17] have been reported. The smart
replacing the use of highly toxic phosgene and carbon monoxide in 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-
* Corresponding author. Fax: +82 63 270 3408.
rus ylide CO2 adducts [21], and super-bases [22] recently joined to
** Corresponding author. Fax: +82 43 267 2279.
E-mail addresses: jeunggonkim@jbnu.ac.kr (J.G. Kim), ykim@chungbuk.ac.kr the list of metal and halide free CO2 xation catalysts.
(Y. Kim).
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 211
Experimental
General considerations
Scheme 2. Chemical structures of amine compounds in this work and their designations.
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.
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 volume). Then, CO2 was charged in the reactor and the pressure
and CO2 was adjusted to desired pressure at appropriate temperature. The
reactor was maintained for the desired time. After then, the
The cycloaddition reaction of CO2 to epoxide was carried out pressure reactor was cooled to ambient temperature, and the
by charging a stirring bar, epoxide (10 mmol), and catalyst excess CO2 was vented. A small sample of mixture was taken for
(10 mmol), into a stainless steel pressure reactor (10 mL inner 1
H NMR analysis.
214 W. Cho et al. / Journal of Industrial and Engineering Chemistry 44 (2016) 210215
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