Transformation of CO2 into α-Alkylidene Cyclic Carbonates at Room

Feb 26, 2019 - University of Chinese Academy of Sciences , 19A Yuquan Road, Shijingshan District, ... Ionic liquids with the biomass-derived anion com...
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Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Transformation of CO2 into α‑Alkylidene Cyclic Carbonates at Room Temperature Cocatalyzed by CuI and Ionic Liquid with BiomassDerived Levulinate Anion Yue Hu,†,‡ Jinliang Song,*,† Chao Xie,†,‡ Haoran Wu,†,‡ Tao Jiang,*,† Guanying Yang,† and Buxing Han*,†,‡

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†

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, No. 2 Zhongguancun North First Street, Haidian District, Beijing 100190, People’s Republic of China ‡ University of Chinese Academy of Sciences, 19A Yuquan Road, Shijingshan District, Beijing 100049, People’s Republic of China S Supporting Information *

ABSTRACT: Utilization of carbon dioxide (CO2) as a renewable C1 building block is of great importance. Herein, a series of ionic liquids (ILs) with biomass-derived anions or/and cations were synthesized, and using these prepared ILs as catalytic solvents, CuI could catalyze carboxylative cyclization of propargylic alcohols with CO2 at room temperature (25 °C). Especially, the IL [Bu4P][Levulinate] with cellulose-derived levulinate anion combined with CuI showed the best performance, affording various corresponding α-alkylidene cyclic carbonates in good yields (>90%). In the reaction, CuI and [Bu4P][Levulinate] played synergistic role to activate the CC and hydroxyl groups in propargylic alcohols, respectively, leading to the excellent performance of CuI/[Bu4P][Levuliniate]. Additionally, the CuI/[Bu4P][Levuliniate] catalytic system could be reused for five times without noticeable decrease in activity and selectivity. KEYWORDS: Transformation of carbon dioxide, α-Alkylidene cyclic carbonates, Ionic liquids, Cellulose-derived levulinic acid, Carboxylative cyclization

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INTRODUCTION

mild, efficient and sustainable catalytic systems for this carboxylative cyclization reaction. Ionic liquids (ILs) as a group of functional solvents have been applied in many areas, especially as catalysts for diverse reactions.29−35 Recently, significant achievements have been obtained for CO2 capture and transformation using IL systems due to the unique properties of ILs.36−43 For the carboxylative cyclization of CO2 with propargylic alcohols, several IL systems, such as CuCl/[BMIm][PhSO3],44 AgOAc/(nC 7 H 15 ) 4 NBr, 15,16 AgI/[Emim]OAc, 20 and [Bu 4 P] 3 [2,4OPym-5-Ac],45 etc., have been employed. Despite these progresses, there were still some limitations for these ILcatalytic systems, such as the high reaction temperature (120 °C),44 the use of noble Ag species,15,16,19,20 and the special precursor to synthesize ILs,15,16,45 etc. Thus, design of novel ILs with high efficiency for the titled CO2 conversion is still a long-term task, and the designability of ILs provides many opportunities and great potential to realize CO2 transformation efficiently and sustainably.

The emission of carbon dioxide (CO2) is one of the most challenging issues faced by mankind. In another aspect, CO2 has been recognized as a nontoxic, renewable and abundant C1 resource.1−6 Innovative and sufficient utilization of this important C1 resource is of great importance for a sustainable future. In this context, chemical transformation of CO2 has gained significant attention, and various value-added chemicals have been successfully synthesized by employing CO2 as a C1 building block.7−11 Among diverse strategies for CO2 conversion, the carboxylative cyclization of propargylic alcohols with CO2 is one of the most promising routes because the products α-alkylidene cyclic carbonates can be used to synthesize fine chemicals and pharmaceuticals.12 Until now, various catalysts, including organic13,14 and metal (i.e., Ag,15−20 Zn,21 Pd,22,23 W,24 Co,25 and Cu26−28) ones, have been developed for the carboxylative cyclization of CO2 with propargylic alcohols. However, these reported catalytic systems suffered from some drawbacks (e.g., harsh reaction conditions, catalyst recyclability, and use of organic solvents or bases) needing to be overcome further. Therefore, it is highly desired to develop © XXXX American Chemical Society

Received: November 10, 2018 Revised: February 18, 2019 Published: February 26, 2019 A

DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Letter

ACS Sustainable Chemistry & Engineering Herein, a IL ([Bu4P][Levulinate]) with the biomass-derived levulinate anion was prepared by the simple neutralization of tetrabutylphosphonium hydroxide ([Bu4P]OH) and cellulosederived levulinic acid.46 The catalytic system consisting of CuI and [Bu4P][Levulinate] showed outstanding performance for the carboxylative cyclization of propargylic alcohols with CO2 at room temperature (25 °C) without using any organic bases or solvents, affording various α-alkylidene cyclic carbonates in good to excellent yields.

Table 2. Effect of Various ILs on the Carboxylative Cyclization of CO2 with 2-Methyl-3-butyn-2-ol in the Presence of CuIa

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RESULTS AND DISCUSSION The carboxylative cyclization of CO2 with 2-methyl-3-butyn-2ol was initially selected as a model reaction to evaluate the

Salt

IL

Yield (%)b

1 2 3 4 5 6 7 8 9 10c 11d

None Cu(OAc)2·H2O CuSO4 Cu(OTf)2 CuCl CuCl2 CuI AgOAc CuI CuI CuI

[Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] [Bu4P][Levulinate] None [Bu4P][Levulinate] [Bu4P][Levulinate]

18 48 60 74 84 88 97 98 0 55 77

IL

Yield (%)b

1 2 3 4 5 6 7 8

[Ch][Isonicotinate] [Ch]2[2,5-Furandicarboxylate] [Bu4P][Isonicotinate] [Bu4P]2[2,5-Furandicarboxylate] [Bu4P][Lactate] [Ch][Levulinate] [Bu4N][Levulinate] [Bu4P][Levulinate]

6 17 63 88 65 93 90 97

a

Reaction conditions: 2-methyl-3-butyn-2-ol, 2 mmol; CuI, 0.04 mmol; IL, 0.5 g; CO2, 1 MPa; 25 °C; 4 h. bYields were determined by 1 H NMR using 1,3,5-trioxane as the internal standard.

Table 1. Activity of Various Copper Salts Combined with [Bu4P][Levulinate] for the Carboxylative Cyclization of CO2 with 2-Methyl-3-butyn-2-ola Entry

Entry

those with oxygen acid anions (Table 1, entries 2−4), and meanwhile, CuI showed better performance than CuCl and CuCl2 because the dissociation of iodide anion with copper ion was more facile than that of chloride anion with copper ion,21 and thus, the copper ion in CuI had stronger ability to activate the triple bond in the propargylic alcohols than those in CuCl and CuCl2, which was beneficial for the occurrence of the carboxylative cyclization. It should be pointed out that the byproduct α-hydroxy ketone could be generated via the hydrolysis of the obtained α-alkylidene cyclic carbonate47 due to the minor amount of water in IL and the salts. Furthermore, CuI showed no activity in the absence of [Bu4P][Levulinate] (Table 1, entry 9), indicating the synergistic effect of CuI and [Bu4P][Levulinate]. Additionally, the activity decreased when the amount of CuI or IL was decreased to 1 mol % (Table 1, entry 10) and 0.1 g (Table 1, entry 11), respectively. To show the unique role of [Bu4P][Levulinate], several other ILs based on biomass derivatives were synthesized for comparison (Scheme 1). It was found that both the anion and cation of ILs played important role on the carboxylative cyclization of CO2 with 2-methyl-3-butyn-2-ol (Table 2). The CuI/[Ch][Isonicotinate] and CuI/[Ch][2,5-Furandicarboxylate] showed very low activity (Table 2, entries 1 and 2). In contrast, CuI/[Bu4P][Isonicotinate] and CuI/[Bu4P][2,5Furandicarboxylate] systems showed much higher catalytic activity (Table 1, entries 3 and 4), indicating the key role of the anions. Meanwhile, CuI/[Bu4P][Lactate] only provided a product yield of 65% (Table 2, entry 5). More importantly, all the ILs derived from levulinic acid showed higher activity (Table 2, entries 6−8) than the ILs with the same cations, and CuI/[Bu4P][Levulinate] possessed the best performance with a product yield of 97% (Table 2, entry 8). There were several advantages for this CuI/[Bu4P][Levulinate] catalytic system, including relative lower price of CuI than AgOAc, avoiding the use of equivalent organic bases, and the ease in recyclability of the entire catalytic system. The above results suggested the priority of CuI/[Bu4P][Levulinate] catalytic system for the carboxylative cyclization of CO2 with propargylic alcohols. In addition, the activity of this CuI/[Bu4P][Levulinate] catalytic system was comparable or even higher than the reported Agcontaining IL-based catalytic systems (Table S1, entries 1−5), and the reaction conditions in this work was milder than most of Ag-free catalytic systems (Table S1, entries 6−15). Although the reaction conditions of CuI/[Bu4P][Levulinate] system were comparable with those for [Bu4P]3[2,4-OPym-5-Ac] (Table S1, entries 9 and 17), the synthesis of [Bu4P]3[2,4-

a

Reaction conditions: 2-methyl-3-butyn-2-ol, 2 mmol; Cu salts, 0.04 mmol; [Bu4P][Levulinate], 0.5 g; CO2, 1 MPa; 25 °C; 4 h. bYields were determined by 1H NMR using 1,3,5-trioxane as the internal standard. cCuI, 0.02 mmol. dIL, 0.1 g.

Scheme 1. Structure of Cations and Anions of the Synthesized ILs

catalytic activity of various metal salts dissolved in [Bu4P][Levulinate] (Table 1). When only [Bu4P][Levulinate] was employed (Table 1, entry 1), the yield for the desired product was very low (18%). In comparison, the catalytic activity was improved when some copper salts were applied with [Bu4P][Levulinate] (Table 1, entries 2−7), and CuI/[Bu4P][Levulinate] showed the best performance with a product yield of 97% (Table 1, entry 7), and the activity was comparable with that of AgOAc (Table 1, entry 8). Based on the results shown in Table 1, the anions in copper salts could significantly affect the activity of the studied reaction. The copper salts with halogen anions (Table 1, entries 5−7) had higher activity than B

DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

Table 3. Carboxylative Cyclization of CO2 with Various Propargylic Alcohols over CuI Using [Bu4P][Levulinate] as the Catalytic Solventa

a Reaction conditions: substrate, 2 mmol; CuI, 0.04 mmol; [Bu4P][Levulinate], 0.5 g; CO2, 1 MPa; 25 °C. bYields were determined by 1H NMR using 1,3,5-trioxane as the internal standard.

OPym-5-Ac] needed a complicated precursor (2,4-dihydroxypyrimidine-5-carboxylic acid),45 while [Bu4P][Levulinate] was prepared using cellulose-derived levulinic acid, suggesting the advantage of [Bu4P][Levulinate] to some extent. The influence of other reaction parameters were further studied using CuI/[Bu4P][Levulinate] as an efficient catalytic solvent. The product yield increased with the prolonged reaction time at 25 °C (Figure S2), and the reaction was completed in 4 h with a yield of 97%. Moreover, at higher pressure, more CO2 dissolved in the ILs, which could increase the interaction probability between CO2 with the catalyst and the propargylic alcohols. Therefore, higher CO2 pressure was beneficial for the reaction (Figure S3), and 1 MPa was selected as the optimal pressure. Meanwhile, it was found that a product yield of 75% could be achieved at ambient conditions (25 °C, 0.1 MPa CO2) in CuI/[Bu4P][Levulinate] system with a reaction time of 16 h (Table S1, entry 17), further verify the high activity of the CuI/[Bu4P][Levulinate] system. More importantly, CuI/[Bu4P][Levulinate] catalytic system could be reused at least for 5 times without dramatic loss in activity and

Figure 1. 1H NMR spectra of 2-methyl-3-butyn-2-ol, mixture of 2methyl-3-butyn-2-ol and IL ([Bu4P][Levulinate]), mixture of 2methyl-3-butyn-2-ol and CuI, and mixture of 2-methyl-3-butyn-2-ol, IL and CuI.

C

DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering Scheme 2. Proposed Reaction Pathway of the Carboxylative Cyclization of CO2 and Propargylic Alcohols in CuI/ [Bu4P][Levulinate] Catalytic System

selectivity (Figure S4) although the oxidation degree of Cu+ to Cu2+ was increased from 4% to 41% as detected by XPS examination (Figure S5) after the catalytic system was reused for five cycles. Furthermore, the recyclability of the catalytic system after 2 h was examined (Figure S4b), and no obvious difference was found in the five cycles. Additionally, CuCl and CuCl2 showed similar activity for the reaction (Table 1, entries 5 and 6). These results indicated the valence of Cu had negligible effect on the activity of CuI/[Bu4P][Levulinate] system. In the catalytic cycle, both Cu2+ and Cu+ played the role of activating the triple bond in the propargylic alcohols to enhance the reaction. Delighted by the excellent performance of CuI/[Bu4P][Levulinate] for the reaction between CO2 and 2-methyl-3butyn-2-ol, the possibility of the carboxylative cyclization of CO2 with other propargylic alcohols was explored (Table 3). As expected, CuI/[Bu4P][Levulinate] also showed very good activity for other propargylic alcohols, and good to excellent yields of the corresponding α-alkylidene cyclic carbonates could be achieved (Table 3, entries 1−7). It was found that the steric hindrance of the substituted groups affected the reactivity significantly. The substrates with methyl, ethyl and isobutyl groups had higher reactivity (Table 3, entries 1−3) than those with cyclic alkyl and phenyl substituted groups (Table 3, entries 4−6), which needed a prolonged time to reach satisfactory yields. Notably, CuI/[Bu4P][Levulinate] showed much higher activity for the propargylic alcohol with electron-withdrawing group (Table 3, entry 7) than the reported systems.45 To confirm the specific role of [Bu4P][Levulinate] and CuI in the reaction process, the interactions of CuI, [Bu4P][Levulinate], and 2-methyl-3-butyn-2-ol were examined by 1H NMR examinations. First, the H signal for the O−H in 2methyl-3-butyn-2-ol disappeared in the system containing

[Bu4P][Levulinate] (Figure 1), while it only shifted from 5.29 to 5.30 ppm in the mixture of CuI and 2-methyl-3-butyn-2-ol (Figure S6). These results indicated that [Bu4P][Levulinate] played the dominant role to activate the hydroxyl group in the 2-methyl-3-butyn-2-ol via hydrogen bonding between the hydroxyl group and the carbonyl and carboxyl groups in IL, and these interactions could improve the insertion ability of CO2,17,45 which was of vital importance in the carboxylative cyclization. In the FT-IR spectrum (Figure S7), it was found that the peak at 3300 cm−1 for hydroxyl groups became weaker in the presence of IL, further indicating that the hydroxyl group was activated by IL. Second, the H signal for HCC showed a downfield shift from 3.10 to 3.17 ppm in CuI containing systems, while it was a very small upfield shift from 3.10 to 3.09 ppm in the mixture of IL and 2-methyl-3-butyn-2ol (Figure S8), indicating the very weak interaction between the IL and the H on the HCC group. These results verified that the CC bonds was dominantly activated by CuI, resulting in the electron redistribution of alkynyl carbon,45 which might facilitate the nucleophilic attack of the polycarbonate intermediate (Scheme 2) on the triple bond. Third, obvious change of 1H NMR for CH2 near carbonyl and carboxyl groups was observed between the pure IL and the mixture of IL and CuI (Figure S9), indicating the strong interaction between CuI and IL (carbonyl and carboxyl groups), which could enhance the catalytic activity of CuI. In order to confirm the role of carbonyl groups, some control experiments were carried out (Table S2). Acetone and acetonylacetone could improve the catalytic activity of CuI/ DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) (Table S2, entries 2 and 3), while no catalytic role of acetone and acetonylacetone was found without DBU, proving the enhancing effect of the carbonyl groups for CuI activity (Table S2, entries 4 and 5). Meanwhile, [Bu4P][Valeriate] D

DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

ACS Sustainable Chemistry & Engineering

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without carbonyl group showed a lower activity (Table S2, entry 6) than [Bu4P][Levulinate] with carbonyl group because the coordination of carbonyl group with Cu+ could improve the dissociation of Cu+ and I−, which could increase the ability of Cu+ to activate the triple bond in the propargylic alcohols, and thus better performance was achieved in CuI/[Bu4P][Levulinate] catalytic system. On the basis of the above discussion, the hydroxy groups and CC groups were mainly activated by IL and CuI to enhance the insertion of CO2 and the nucleophilic attack of the polycarbonate intermediate on the triple bond, respectively. In addition, the interaction of CuI and IL could further enhance the catalytic ability of CuI. Based on the above investigations and some reported knowledge,20,21,45,48 a reasonable reaction pathway was proposed for the carboxylative cyclization of CO2 and propargylic alcohols in CuI/[Bu4P][Levulinate] catalytic system (Scheme 2). Initially, the hydroxyl groups were activated via the hydrogen bonding between the hydroxyl group in the propargylic alcohol and the cations in the IL, which was helpful for the insertion of CO2 via electrophilic attack to generate an alkylcarbonate anion. Meanwhile, the carbonyl and carboxyl groups in [Bu4P][Levulinate] could coordinate with Cu+ in CuI to improve the dissociation of I− from Cu+, which could increase the catalytic activity of Cu+, and then the coordinated Cu+ activated the triple bond, which was beneficial for the attack of the O atom in the formed alkylcarbonate anion to the carbon in CC bonds, resulting in the formation of five-membered ring. Finally, the corresponding α-alkylidene cyclic carbonate was obtained with the release of the catalyst.

AUTHOR INFORMATION

Corresponding Authors

*J. Song. E-mail: [email protected]. *T. Jiang. E-mail: [email protected]. *B. Han. E-mail: [email protected]. ORCID

Jinliang Song: 0000-0001-9573-600X Buxing Han: 0000-0003-0440-809X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (21733011, 21890761, 21673248), National Key Research and Development Program of China (2017YFA0403003), Key Research Program of Frontier Sciences of CAS (QYZDY-SSW-SLH013), and Youth Innovation Promotion Association of CAS (2017043).

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REFERENCES

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CONCLUSIONS In summary, a IL ([Bu4P][Levulinate]) with the biomassderived levulinate anion was successfully synthesized using cellulose-derived levulinic acid. CuI/[Bu4P][Levulinate] catalytic system could efficiently catalyze the carboxylative cyclization of propargylic alcohols and CO2 at 25 °C, and various desired α-alkylidene cyclic carbonates with good yields could be generated. Meanwhile, CuI/[Bu4P][Levulinate] could be easily recycled without notable loss in activity. Mechanism study indicated that CuI and [Bu4P][Levulinate] had the synergistic effect for promoting the reaction, in which [Bu4P][Levulinate] activates the hydroxyl groups in propargylic alcohols while CuI activates the CC bonds. We postulate that this green and mild route has great potential of applications in CO2 transformation to produce α-alkylidene cyclic carbonates.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b05851. Experimental section, activity comparison, effect of reaction time and CO2 pressure, recyclability experiment, 1H NMR spectra to determine the interaction between the catalyst and the reactants, FT-IR spectrum, activity of different catalysts, and 1H NMR and 13C NMR spectra for [Bu4P][Levuliniate] and the products (PDF) E

DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

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DOI: 10.1021/acssuschemeng.8b05851 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX