PAPER www.rsc.org/greenchem | Green Chemistry

Synthesis of cyclic carbonates from epoxides and CO2 catalyzed bypotassium halide in the presence of b-cyclodextrin

Jinliang Song, Zhaofu Zhang, Buxing Han,* Suqin Hu, Wenjing Li and Ye Xie

Received 29th August 2008, Accepted 7th October 2008First published as an Advance Article on the web 4th November 2008DOI: 10.1039/b815105a

Development of efficient, cheap and non-toxic catalysts for cycloaddition of CO2 with epoxides toproduce five-membered cyclic carbonates under greener reaction conditions is still a veryattractive topic. In this work, cycloaddition of CO2 with propylene oxide (PO) to propylenecarbonate (PC) catalyzed by potassium halide (KCl, KBr, and KI) in the presence ofb-cyclodextrin was studied at various conditions. It was discovered that potassium halide andb-cyclodextrin (b-CD) showed excellent synergetic effect in promoting the reactions, andKI-b-CD catalytic system was the most efficient among them. The optimal temperature for thereaction was around 120 ◦C, and the reaction rate reached maximum at about 6 MPa at thistemperature. The reaction could be completed in 4 h with very high selectivity. The decrease of theyield of PC was not noticeable after KI-b-CD was reused five times, indicating that the catalystwas very stable. KI-b-CD catalytic system was also very active and selective for cycloaddition ofCO2 with other epoxides, such as glycidyl phenyl ether, epichlorohydrin, and styrene oxide. Themechanism for the synergetic effect is discussed.

Introduction

Chemical conversion of carbon dioxide (CO2) into usefulorganic compounds has attracted much attention in recent yearsbecause CO2 is an inexpensive, nontoxic, and abundant C1

feedstock.1–3 Cycloaddition of CO2 with epoxides to producefive-membered cyclic carbonates is one of the most successfulroutes because cyclic carbonates can be used as aprotic polarsolvents, precursors for producing polycarbonates, fine chemicalingredients, etc.4–8 Numerous catalysts have been developed forthe coupling reaction of CO2 and epoxides, such as alkali metalsalts,9–11 metal oxides,12,13 transition metal complexes,14–17 Schiffbase,18,19 ion-exchange resins,20 functional polymers,21,22 quater-nary ammonium and phosphonium salts,23–26 ionic liquids,27,28

lanthanide oxychloride,29,30 gold nanoparticles supported onresins.31 However, many of these catalyst systems suffer from lowcatalyst stability or reactivity, the need for cosolvent, extremeconditions.

Among the above catalysts, alkali metal salts are an importanttype of catalyst for the cycloaddition of CO2 with epoxides.9–11

Endo et al.10 reported that alkali metal salts could be used ascatalyst for the synthesis of cyclic carbonates using crown etheras co-catalyst. Although the reaction could be conducted at lowtemperature (100 ◦C) and low CO2 pressure, organic solvent,N-methylpyrrolidinone (NMP), was used and crown ether wasa toxic reagent. Recently, Huang et al.11 described that alkalimetal salts could catalyze cycloaddition of CO2 with epoxideseffectively in the presence of PPh3 and phenol without solvents.

Beijing National Laboratory for Molecular Sciences (BNLMS), Centrefor Molecular Science, Institute of Chemistry, Chinese Academy ofSciences, Beijing, 100190, China. E-mail: hanbx@iccas.ac.cn;Fax: 86-10-62562821

In recent years, using b-cyclodextrin (b-CD) as reactioncatalyst has gained much interest.32,33 b-CD, which is a cyclicoligosaccharide consisting of seven glucose units (Scheme 1),exerts a microenvironmental effect that can lead to selectivereactions. b-CD catalyzes reactions by supermolecular catalysisthrough noncovalent bonding. Some catalytic reactions canbe carried out in the presence of b-CD.34–42 Surendra et al.43

reported that b-CD and epoxides could form a cyclodextrin-epoxide complex through hydrogen bonding, which couldactivate the epoxides.

Scheme 1 General structure of b-cyclodextrin.

Development of efficient catalysts for cycloaddition of CO2

with epoxides using cheap and non-toxic reagents and con-ducting the reactions under solvent-free conditions is still anattractive topic. In this work, we conducted the reactions usingpotassium halide as the catalysts in the presence of b-CDunder solvent-free conditions, and discovered that the salts andb-CD showed excellent synergetic effect for the reactions. To ourknowledge, this is the first work to combine these two kinds ofcompounds for the reactions. We believe that the simple, cheaper,and ecologically safer route to synthesize cyclic carbonates hasgreat potential in industrial application.

This journal is © The Royal Society of Chemistry 2008 Green Chem., 2008, 10, 1337–1341 | 1337

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Table 1 Coupling of CO2 and PO catalyzed by different catalystsa

Entry Catalyst Yield (%)c

1 None 02b b-CD 03 KCl 04 KBr 35 KI 276b KCl + b-CD 47b KBr + b-CD 488b KI + b-CD 98

a Typical reaction conditions: a stainless reactor of 22 ml, 20 mmolPO with 2.5 mol% catalyst, CO2 pressure 6 MPa, reaction temperature120 ◦C, reaction time 4 h. b 0.1 g b-CD was added. c Yields weredetermined by GC versus an internal standard.

Results and discussion

Effect of catalysts

The activity of various catalysts was tested using the reactionof PO and CO2 to produce propylene carbonate (PC), and theresults are summarized in Table 1. No product was detectedwithout catalyst or when b-CD only was used as the catalyst(entries 1, 2). Potassium halide could catalyze the cycloadditionalone, but the yield of PC was very low (entries 3–5). Whenb-CD was added, the yield of PC was enhanced (entries 6–8). Ithas been reported by Shi11 that the epoxy ring can be activatedthrough the forming of hydrogen binding with phenol. In oursystem, hydrogen bonding exists between b-CD and epoxides43

(Scheme 2), and this could be the reason that the yield of PCincreased dramatically when b-CD was added. The order ofthe activity of potassium halide was found to be KI > KBr >

KCl (entries 3–5, 6–8), which is consistent with the order ofthe nucleophilicity of the halide ions. Furthermore, the leavingability of the halide anions is another important factor, whichhas great influence on the catalytic activity, and the activityincreases with the leaving ability. The leaving ability of the halideanions is I- > Br- > Cl-, which is consistent with the order of thenucleophilicity of these anions.10,44 Therefore, KI was selected asthe catalyst to study the effect of reaction conditions on thereaction in the presence of b-CD.

Scheme 2 Cyclodextrin-epoxide complex formed through hydrogenbonding.

Effect of CO2 pressure on the yield of PC

Fig. 1 shows the effect of CO2 pressure on the yield of PC at120 ◦C with a reaction time of 2 h. The yield of PC stronglydepended on CO2 pressure. The yield increased with increasingpressure in the low pressure range and reached a maximum

Fig. 1 Effect of CO2 pressure on PC yield. Reaction condition: 20 mmolPO with 2.5 mol% KI, 0.1 g b-CD, reaction temperature 120 ◦C, reactiontime 2 h.

at about 6 MPa, and then decreased further with increasingpressure. In this work, it was observed that there were twophases in the reaction system by using a view cell reportedpreviously.45 The top phase was a CO2-rich phase and the bottomphase was a PO-rich phase. The concentration of the CO2 in thebottom phase increased with increasing pressure, and this wasthe reason that the yield of PC increased with increasing pressureat low pressure. However, too high CO2 pressure causes a lowconcentration of the epoxide in the vicinity of the catalyst, andmay retard the interaction between epoxide and the catalyst,46

resulting in a low yield of the product. Therefore, the optimizedCO2 pressure for our catalyst system was 6 MPa.

Influence of reaction temperature on PC yield

Fig. 2 demonstrates the dependence of the yield of PC ontemperature at CO2 pressure of 6 MPa in the temperature rangeof 100–140 ◦C, and the reaction time was 4 h. It was shownthat the activity of the catalyst was strongly affected by thereaction temperature. The yield of PC increased with increasingtemperature, and reached 98% at 120 ◦C, then the PC yield keptalmost constant with further increase of temperature, hintingthat 120 ◦C is the optimal temperature for the reaction.

Fig. 2 Influence of reaction temperature on PC yield. Reactioncondition: 20 mmol PO with 2.5 mol% KI, 0.1 g b-CD, CO2 pressure6 MPa, reaction time 4 h.

Influence of reaction time

The dependence of the yield of PC on reaction time is presentedin Fig. 3. The reaction was performed in the presence of 2.5 mol%

1338 | Green Chem., 2008, 10, 1337–1341 This journal is © The Royal Society of Chemistry 2008

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Fig. 3 The dependence of PC yield on reaction time. Reactionconditions: 20 mmol PO with 2.5 mol% KI, 0.1 g b-CD, CO2 pressure6 MPa, reaction temperature 120 ◦C.

catalyst KI and 0.1 g b-CD at 120 ◦C under CO2 pressure 6 MPa.In a relatively short reaction time, the conversion of PO wasincomplete and the PC yield was low. It can be seen that a yieldof 98% could be achieved at 4 h. No further increase in the yieldsof PC was observed with prolonged reaction time. Therefore, thereaction time of 4 h was suitable for this system.

Catalyst recyclability

The reusability of the catalyst was also examined using PO as thesubstrate at the optimized reaction conditions and the resultsare shown in Fig. 4. The decrease of the yield of PC was notconsiderable after reused five times, indicating that the catalystwas very stable.

Fig. 4 Reuse of the catalyst. Reaction condition: 20 mmol PO with2.5 mol% KI, 0.1 g b-CD, CO2 pressure 6 MPa, reaction temperature120 ◦C, reaction time 4 h.

Various Substrates

Using KI as the catalyst in the presence of b-CD, cycloadditionof CO2 with other epoxides (Scheme 3) were also studied at120 ◦C and 6 MPa without using any solvent and the resultsare summarized in Table 2. The catalyst system was foundto be applicable to a variety of terminal epoxides, producingthe corresponding cyclic carbonates with yields of 93–99%.Propylene oxide (1a, Table 1) and glycidyl phenyl ether (1b)gave cyclic carbonates in nearly 100% yield. Epichlorohydrin(1c) showed less activity and required a longer time (8 h) to giveproduct 2c in a high yield (93%), which may result from thereduced electron density of the epoxide oxygen atom caused bythe electron-withdrawing CH2Cl group. A much longer reaction

Table 2 Various carbonates synthesis catalyzed by KI in the presenceof b-CDa

Entry Epoxides Products Reaction time (h) Yield (%)

1 4 99

1b 2b2 8 93

1c 2c3 12 94

1d 2d4 24 < 3

1e 2e

a Reaction conditions: 20 mmol epoxide with 2.5 mol% KI, CO2 pressure6 MPa, reaction temperature 120 ◦C, 0.1 g b-CD.

time (12 h) was needed to get a high product yield (94%) whenstyrene oxide (1d) was used as substrate, which is probably dueto the low reactivity of its b-carbon center. When cyclohexeneoxide (1e) was used as the reactant, the yield was very low eventhe reaction time was prolonged to 24 h. This may partially resultfrom the weak interaction between cyclohexene oxide and b-CDdue to the high steric hindrance of cyclohexene oxide and b-CDin our catalytic system. The low activity of cyclohexene oxide47

also contributed the low yield.

Scheme 3 Coupling of CO2 with different epoxides.

Mechanism

It has been suggested by Huang and Shi11 that hydrogen bindingcan activate the ring-opening reaction of epoxides. In ourcatalyst system, there was a hydrogen bonding donor (b-CD).Based on the results discussed above, we propose a possiblemechanism for the formation of cyclic carbonates, which isshown in Scheme 4. Firstly, the coordination of PO withb-CD through hydrogen bonding to form the cyclodextrin-epoxide complex (a in Scheme 4) and this step can activate theepoxy ring. Secondly, the I- anion of KI attacks the less hinderedcarbon atom of the activated ring, followed by ring openingreaction step (b in Scheme 4). Then, the interaction was occurredbetween the oxygen anion of the opened epoxy ring and CO2 andthis can form an alkylcarbonate anion (c in Scheme 4), which

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Scheme 4 The plausible reaction mechanism for the cycloaddition ofCO2 with epoxide catalyzed by KI and b-CD.

is stabilized via the hydrogen bonding. Finally, correspondingcyclic carbonates are achieved through the intramolecular cyclicstep, and meanwhile, the catalyst is regenerated. From thediscussion above, we think that the synergistic effect of iodideanion and b-CD may be the main reason for the high catalyticactivity of the catalyst system.

Conclusions

We found that cyclic carbonates can be formed in high yield fromthe reaction of epoxides with CO2 in the presence of catalyticamounts of KI and b-CD without using any organic solvent.In the KI-b-CD catalytic system, KI is the active catalyst andb-CD acted as a hydrogen bonding donor to accelerate thering-opening reaction, and they show excellent synergetic effectto catalyze the reactions. The catalytic system can be reusedat least five times without noticeable decrease in activity andselectivity. The greener, inexpensive, active, selective and stablecatalytic system has potential application for synthesizing cycliccarbonates from CO2 and epoxides.

Experimental

Materials

CO2 was supplied by Beijing Analytical Instrument Factorywith a purity of 99.995%. Propylene oxide, epichlorohydrin,b-cyclodextrin, potassium iodide, potassium chloride, potas-sium bromide were analytical grade and produced by BeijingChemical Reagents Company. Other epoxides were purchasedfrom ACROS ORGANICS. All chemicals were used as received.

Cycloaddition reaction

All the cycloaddition reactions were conducted in a 22 mLstainless steel reactor equipped with a magnetic stirrer. Wedescribe the procedures for the cycloaddition of propylene oxide(PO) because the procedures for reactions of other epoxidesare similar. In the experiment, desired amounts of catalyst,b-cyclodextrin and PO were added into the reactor. The reactorwas sealed and put into a constant-temperature air bath ofdesired temperature. CO2 was then charged into the reactor until

the desired pressure was reached, and the stirrer was started.After a certain time, the reactor was placed into ice water andCO2 was released slowly passing through a cold trap containingethyl acetate to absorb the trace amount of reactant and productentrained by CO2. After depressurization, ethyl acetate in thecold trap and internal standard dodecane were added into thereactor. The reaction mixture was analyzed by GC (Agilent6820) equipped with a flame-ionized detector. The purity andstructure of the product at some typical experimental conditionswere also checked by 1H NMR and GC-MS. The products ofother epoxides were analyzed at room temperature on a Bruker400 MHz 1H NMR spectrometer using CDCl3 as the solvent. Inthe experiments to test the reusability of the catalyst, the catalystwas recovered by centrifugation, washed using ethyl ether toremove the product and dodecane, and then dried under vacuumfor 12 h at 60 ◦C before reused. Spectral characterizations of theproducts (2b–d) are as follows:

4-Phenyloxymethyl-1,3-dioxolan-2-one (2b). 1H NMR(CDCl3, 400 MHz) d (ppm) 4.15 (dd, J = 3.6, 10.5 Hz, 1H),4.24 (dd, J = 4.4, 10.5 Hz, 1H), 4.54 (dd, J = 6.0, 8.5 Hz, 1H),4.62 (t, J = 8.4 Hz, 1H), 5.00–5.05 (m, 1H), 6.91 (d, J = 8.2 Hz,2H), 7.02 (t, J = 7.4 Hz, 1H), 7.31 (t, J = 8.2 Hz, 2H).

4-Chloromethyl-1,3-dioxolan-2-one (2c). 1H NMR (CDCl3,400 MHz) d (ppm) 3.75 (dd, J = 3.6, 12.3 Hz, 1H), 3.84 (dd,J = 4.9,12.3 Hz, 1H), 4.42 (dd, J = 5.7,8.8 Hz, 1H), 4.62(t, J = 8.7 Hz, 1H), 5.00–5.06 (m, 1H).

4-Phenyl-1,3-dioxolan-2-one (2d). 1H NMR (CDCl3, 400MHz) d (ppm) 4.35 (t, J = 8.2 Hz, 1H), 4.80 (t, J = 8.4 Hz,1H), 5.68 (t, J = 8.0 Hz, 1H), 7.36–7.45 (m, 5H).

Acknowledgements

This work was supported by the National Key Basic ResearchProject of China (2006CB202504) and Chinese Academy ofSciences (KJCX2.YW.H16).

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