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Int. J. Mol. Sci. 2014, 15(6), 9945-9951; doi:10.3390/ijms15069945

Communication
2,2',2''-Terpyridine-Catalyzed Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide under Solvent-Free Conditions
Huixin Liu , Renqin Zeng and Ruimao Hua *
Department of Chemistry, Tsinghua University, Beijing 100084, China; E-Mails: liuhuixin9015@163.com (H.L.); zengrq@mails.tsinghua.edu.cn (R.Z.)
*
Author to whom correspondence should be addressed; E-Mail: ruimao@mail.tsinghua.edu.cn; Tel.: +86-10-6279-2596; Fax: +86-10-6277-1149.
Received: 10 March 2014; in revised form: 15 April 2014 / Accepted: 16 May 2014 /
Published: 4 June 2014

Abstract

: An efficient coupling reaction of epoxides with CO2 affording cyclic carbonates with the use of 2,2',2''-terpyridine as catalyst under solvent-free conditions has been developed.
Keywords:
carbon dioxide; epoxide; cyclic carbonates; terpyridine

1. Introduction

The coupling reaction of epoxides with CO2 is an atom-economic and well-known process for the synthesis of five-membered cyclic carbonates (Scheme 1), which have been widely applied as the aprotic polar solvents [1], electrolytes for lithium ion batteries [2], precursors for organic synthesis [3], and polymers [4]. Therefore, a variety of catalytic systems have been reported to catalyze this transformation including alkali metal compounds [5,6,7], ionic liquids [8,9,10], transition metal complexes [11,12,13,14,15], and heterogeneous catalysts [16,17,18,19].

On the other hand, recently, the catalytic reactions based on the use of small organic molecules as catalysts have been greatly developed with the significant advantages of metal-free procedure, lack of sensitivity to moisture and oxygen, affordability, low cost and low toxicity [20,21]. Recently, the reaction between amine and CO2 is considered to be one of the methods for the storage of CO2 [22], and it has been also disclosed that the quaternary ammonium salts [23] and amines [24] are the efficient catalysts for the reaction of epoxides with CO2 to give cyclic carbonates. In addition, our previous work revealed that N,N-dimethylformamide (DMF) could catalyze the same reaction efficiently [25]. In continuation of our interest in developing efficient catalytic systems using simple and cheap organic compounds as catalysts in the coupling reaction of epoxides with CO2, we therefore have investigated the catalytic activity of nitrogen-containing organic compounds such as amines, anilines, amides and pyridines, and found that 2,2',2''-terpyridine is an excellent organocatalyst to provide an alternative metal-free catalytic system for the conversion of CO2 to cyclic carbonates.

Ijms 15 09945 g001 1024
Scheme 1. Synthesis of cyclic carbonates from epoxides and CO2.

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Scheme 1. Synthesis of cyclic carbonates from epoxides and CO2.
Ijms 15 09945 g001 1024

2. Results and Discussion

Table 1 concludes the catalytic activity of a variety of nitrogen-containing organic compounds in the coupling reaction of 1-chloro-2,3-epoxypropane (1a) with CO2 (3.0 MPa of initial pressure) in an autoclave in the presence of 10 mol % of organocatalysts at 130 °C for 20 h under solvent-free conditions. In general, all the used nitrogen-containing compounds showed the catalytic activity to promote the coupling reaction to give the desirable product of 4-cholromethyl-[1,3]dioxolan-2-one (2a) in fair to good yields. As was observed for the formation of 2a, trialkyl tertiary amines of Et3N and Bu3N showed modest catalytic activity to give 2a in 48% and 53% yields, respectively (entries 1,2). Although TEMED (N,N,N',N'-tetramethylethylenediamine), DBU (1,8-diazabicyclo[5.4.0]-undec-7-ene) and DABCO (1,4-diazabicyclo[2.2.2]octane) contains two nitrogen atoms, they displayed the considerable different catalytic activities, and DABCO showed higher catalytic activity due possible to its higher nucleophilicity resulting from the alkyl groups not to disturb the lone pairs (entries 3,4 vs. entry 5). In addition, TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-ene), which has three different nitrogen atoms showed moderate catalytic activity to give 2a in 56% yield (entry 6). In the cases of anilines, the catalytic activity was enhanced by increasing the number of methyl groups to nitrogen atom (entries 7–9). However, unexpectedly, benzamide, N,N-dimethylbenzamide and 2,3,4,5,6-pentafluorobenzamide had similar catalytic activities to catalyze the coupling reaction to give 2a in good yields (entries 10–12). When six-membered N-heterocyclic compounds such as pyridine, 2-methylpyridine and 2-(dimethylamino)pyridine were used, 2a could be obtained in modest to good yields (entries 13–15). 2-Phenylpyrimidine with two nitrogen atoms catalyzed the reaction to afford 2a in 79% yield (entry 16), and the best yield in product 2a was obtained in the presence of 2,2',2''-terpyridine (entry 17). The reason that 2,2',2''-terpyridine had high catalytic activity might be resulted from its unique structure and synergy effects of three pyridyl groups bonded by position 2.

In addition, in order to optimize the catalytic system using 2,2',2''-terpyridine as catalyst, the effect of reaction temperature, catalyst dosage, reaction time and pressure of CO2 were also investigated. As shown in Table 2, the formation of 2a was greatly affected by reaction temperature, and when the reaction was performed at 110 °C, the yield of 2a was greatly decreased to 72% (entry 1). However, at 130 °C, 2a could be obtained in similar yields by either using less amount of catalyst (5.0 mol % (entry 2) or 1.0 mol % (entry 3) vs. entry 16 of Table 1), or decreasing the reaction time from 20 to 10 h (entry 5), although further decreasing the catalyst dosage (0.5 mol % of catalyst, entry 4) and the reaction time (entry 6) or decreasing the pressure of CO2 resulted in the decrease of product yield (entry 7). In addition, increase of CO2 pressure could not improve the yield of 2a (entry 8). Therefore, the reaction conditions indicated in entry 5 of Table 2 are selected as the optimized conditions for the reactions of a variety of epoxides with CO2.

To examine the substrate scope of the present catalytic system, several representative epoxides were subjected to the optimized reaction conditions as shown in Scheme 2, and found that the monoalkyl- and monoaryl-substituted epoxides could undergo the coupling reaction with CO2 giving the corresponding cyclic carbonates in good to high yields. It is worth noting that vinyl-substituted epoxide underwent the reaction smoothly to give the vinyl cyclic carbonate, which is expected to be a useful monomer for synthesis of functional polymer. However, unfortunately, the internal epoxide such as 2,3-epoxybutane and 1,2-epoxycyclohexane showed very low reactivity due possible to their steric hindrance.

Table Table 1. Catalytic activity of nitrogen-containing compounds in the coupling of 1-chloro-2,3-epoxypropane (1a) with CO2 under solvent-free conditions a.

Click here to display table

Table 1. Catalytic activity of nitrogen-containing compounds in the coupling of 1-chloro-2,3-epoxypropane (1a) with CO2 under solvent-free conditions a.
Ijms 15 09945 i001
EntryOrganocatalystYield (%) bEntryOrganocatalystYield (%) b
1Et3N4812F5C6CONH271
2Bu3N5313pyridine59
3TEMED35142-methylpyridine63
4DBU3215 Ijms 15 09945 i00271
5DABCO46
6TBD5616 Ijms 15 09945 i00379
7PhNH259
8PhNHMe70
9PhNMe28117 Ijms 15 09945 i00488
10PhCONH270
11PhCONMe274

a, The reactions were carried out using 5.0 mmol of 1a and 10 mol % of catalyst in a 25-mL autoclave with CO2 at 130 °C for 20 h; b, Yields of 2a are based on GC by using n-C18H38 as internal standard.

The proposed mechanism for the coupling reaction of epoxides with CO2 to produce cyclic carbonates catalyzed by 2,2',2''-terpyridine is shown in Scheme 3. It involves the nucleophilic addition of nitrogen atom(s) of 2,2',2''-terpyridine to CO2, and the ring-opening reaction of epoxide with nucleophilic intermediate via C-O bond cleavage, followed by intramolecular nucleophilic addition to construct the five-membered ring, and finally, to give cyclic carbonate and regenerate catalyst. All the steps are the traditional and well-known transformation.

Table Table 2. Effect of reaction conditions on the formation of 4-cholromethyl-[1,3]dioxolan-2-one (2a) using 2,2',2''-terpyridine as catalyst a.

Click here to display table

Table 2. Effect of reaction conditions on the formation of 4-cholromethyl-[1,3]dioxolan-2-one (2a) using 2,2',2''-terpyridine as catalyst a.
EntryTemp (°C)Catalyst (mol %)Time (h)Pressure (MPa)Yield (%) b
111010203.072
21305203.088
31301203.087
41300.5203.068
51301103.090
6130163.080
71301102.581
81301104.089

a, The reactions were carried out using 5.0 mmol of 1a in a 25-mL autoclave with CO2; b, Yields of 2a are based on GC by using n-C18H38 as internal standard.

Ijms 15 09945 g002 1024
Scheme 2. Coupling reaction of epoxides with CO2 in the presence of 2,2',2''-terpyridine a. a Reactions were carried out using 5.0 mmol of 1 and the yield of 2 is isolated yields.

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Scheme 2. Coupling reaction of epoxides with CO2 in the presence of 2,2',2''-terpyridine a. a Reactions were carried out using 5.0 mmol of 1 and the yield of 2 is isolated yields.
Ijms 15 09945 g002 1024
Ijms 15 09945 g003 1024
Scheme 3. A proposed mechanism for the formation of cyclic carbonate.

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Scheme 3. A proposed mechanism for the formation of cyclic carbonate.
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3. Experimental Section

3.1. General Methods

All organic starting materials and organocatalysts are analytically pure and used without further purification. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECA-300 spectrometer (Tokyo, Japan) using CDCl3 as solvent at 298 K. 1H-NMR (300 MHz) chemical shifts (δ) were referenced to internal standard TMS (for 1H, δ = 0.00 ppm). 13C-NMR (75 MHz) chemical shifts were referenced to internal solvent CDCl3 (for 13C, δ = 77.16 ppm). Mass spectra (MS) were obtained on a Shimadzu GCMS-QP2010S (Shimadzu, Tokyo, Japan).

3.2. A Typical Experiment for the Synthesis of 4-Chloromethyl-[1,3]dioxolan-2-one (2a)

1-Chloro-2,3-epoxypropane (1a) (462.6 mg, 5.0 mmol) and 2,2',2''-terpyridine (0.05 mmol, 1.0 mol %) were charged in a 25 mL-autoclave, and then CO2 was introduced at an initial pressure of 3.0 MPa at room temperature, and the mixture was heated at 130 °C with stirring for 10 h. After the reaction, the autoclave was cooled to room temperature, CO2 was released slowly. To the obtained reaction mixture, 1.0 mmol of octadecane (as an internal standard material for GC analysis) and 4.0 mL of CH2Cl2 were added with stirring, and then the resulting mixture was analyzed by GC and GC-MS. 2a was obtained in 90% yield (614.4 mg, 4.5 mmol) by Kugelrohr distillation. 2ac was isolated by Kugelrohr distillation, and 2df were purified by flash column chromatography on silica gel with petroleum ether as eluent.

All the products (2af) were known compounds and identified by their 1H-NMR, 13C-NMR and GC-MS. As exampled, the characterization data of 2a is reported as follow: 1H-NMR (300 MHz, CDCl3) δ 4.95–5.02 (m, 1H), 4.58 (dd, 1H, J = 8.7, 8.2 Hz), 4.39 (dd, 1H, J = 8.7, 5.8 Hz), 3.79–3.73 (m, 2H); 13C-NMR (75 MHz, CDCl3) δ 154.4, 74.4, 67.1, 44.0; GCMS m/z (% rel. intensity) 136 (M+, 0.5), 87 (100), 62 (14), 57 (9), 49 (13).

4. Conclusions

In summary, 2,2',2''-terpyridine was proven to be an efficient organocatalyst for the coupling reaction of epoxides with CO2 to afford cyclic carbonates under solvent-free and metal-free conditions. The present process represents a simple and green catalytic system for the activation and conversion of CO2 into valuable organic compounds.

Acknowledgments

This project was supported by the National Basic Research Program of China (973 Program, 2011CB201405), and National Natural Science Foundation of China (21032004).

Author Contributions

Both of co-authors did the research work including optimizing the reaction conditions and examining the substrate scope.

Conflicts of Interest

The authors declare no conflict of interest.

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