Organic carbonates as green media: from laboratory syntheses to industrial applications

Abstract

The research on greener solvents is of paramount importance for achieving sustainable processes. To replace traditional hazardous media, green solvents must display negligible environmental effects and biological degradability while being available on a large scale and exhibiting comparable or even superior performances than the currently employed media. In this scenario, organic carbonates (OCs) are among the most prominent candidates as they are commercially available at a reasonable price and offer a broad range of tunable proprieties, making them usable in a wide range of applications. Based on this premise, this review focuses on the use of OCs as green media ranging from laboratory synthetic approaches to industrial applications. According to our literature screening covering the last 40 years, organic carbonates have mostly been investigated as electrolyte solvents (23%), media in organic synthesis (21%) and solvents for the extraction of compounds from different biological and non-biological matrices (13%). Besides, OCs have applications in several other fields spanning from analytical chemistry and biological/biochemical fields to the restoration of ancient artifacts. Most of the OCs used in these applications are dialkyl carbonates (DACs), such as dimethyl carbonate (DMC), propylene carbonate (PC) and ethylene carbonate (EC), which are commercially available at low cost. However, owing to their simple synthetic procedures, new custom-made organic carbonates have been synthetized and used for membrane casting, preparation of polymers and plasticizers, surface modification of materials and as electrolytes in Li-ion batteries. Organic carbonates go beyond simply replacing toxic solvents; they offer an opportunity to transform a variety of processes into sustainable processes. From enhancing the performance of batteries and advancing materials science to driving innovations in green chemistry and improving industrial sustainability, their potential is vast. The adoption of organic carbonates as green media is likely to have far-reaching effects, making them valuable tools for researchers and industries aiming to develop more sustainable processes.

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Giacomo Trapasso

Giacomo Trapasso obtained his Master's degree in Science and Technology of Bio- and Nano-materials in 2020 from Ca’ Foscari University of Venice (Italy). In 2024, he obtained his PhD in Environmental Sciences in co-participation with the Institute of Membrane Technology (ITM-CNR) in Rende (Italy). In 2024, he was awarded for the best PhD thesis in green and sustainable chemistry by the Italian Chemical Society (SCI). In 2024, he was nominated as an IUPAC Young Observer. His research mainly focuses on the development of greener procedures for the synthesis of bio-based platform chemicals, biopolymers, and green solvents.

Fabio Aricò

Fabio Aricò is a Full Professor of Organic Chemistry at the Department of Environmental Sciences and Informatics at Ca’ Foscari University of Venice (Italy), where he is leading a research group working on Green Chemistry. His main research interests are green chemistry biorefinery (C5 and C6 bio-based platform chemicals) and chlorine-free reactions. He has published more than 90 scientific peer-reviewed papers and holds 3 granted patents. In 2019, he was also awarded the Experienced Chemist award by IUPAC-NHU International Award for Advancement in Green Chemistry in recognition of his work on chlorine-free approaches for biorefinery development.

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Green foundation

1. To the best of our knowledge, this is the first comprehensive review specifically focused on organic carbonates as green media ranging from laboratory organic syntheses to industrial applications. As a result, this work is based on an extensive bibliographic research covering the past 40 years.

2. The use of DACs as green solvents is appealing to a broad spectrum of scientific communities, industrial sectors, and policymakers committed to advancing sustainability, reducing environmental impact, and promoting safer chemical practices.

3. DACs offer more than just alternatives to toxic solvents; they present an opportunity to revolutionize various scientific fields towards more sustainable practices. The widespread adoption of DACs as green solvents is likely to have far-reaching effects, making them valuable resources for researchers and industries focused on developing more sustainable processes.

1. Introduction

Following the worldwide increase in environmental awareness, traditional chemical methods are being replaced with new and more sustainable methods, which is also highlighted in the recent European Green Deal (EGD).^1,2 For this, the first and foremost focus should be on the selection and use of solvents. In fact, solvents are responsible for the consumption of more than 60% of the energy required in industrial plants, and they are the most discarded substances in industrial processes, making them one of the major contributors for environmental damage.^3–6 Thus, solvent selection is crucial as it impacts the economics and operation time of the production process in plants.⁷

In this case, several pharmaceutical companies, i.e., Pfizer, GSK, Astra Zeneca and Sanofi, have combined the major solvent selection guides developed thus far.^8,9 The criteria considered are safety (S), occupational health (H), environment (E), quality (risk of impurities in the drug substance), industrial constraints (i.e., boiling point, freezing temperature, density, recyclability) and cost.^9,10

This resulted in a “traffic light” colour code system, where green represents preferred solvents, yellow for compounds showing some health or environmental issues and red for toxic solvents that need to be substituted. Numerous commercially available solvents commonly used in organic synthesis are evidently not recommended owing to their high volatility, flammability, hazardousness and many other health risks.

Considering this, it is necessary to explore more environmentally friendly and tunable solvents that have a negligible environmental effect, are biologically degradable^3,11 and can replace traditional hazardous media in chemical processes. Solvents fulfilling these requirements are called “green” solvents.^3,6,12 A green solvent must possess the characteristics of low vapor pressure, high boiling point, low price, recyclability, non-toxicity, chemical and thermal stability and non-flammability, while possibly being a bio-derived product.^13–15 In addition, a green solvent should be available on a large scale, thus ensuring a stable market production. It must be prepared through energy-saving processes with high atom economy synthetic procedures and should demonstrate comparable or even superior performances to the currently used solvents.¹⁵ A wide-range of green solvents derived from renewable feedstocks are currently accessible including (bio)ethanol, ethyl lactate, 2-methyl-tetrahydrofuran (2-Me-THF), cyclopentyl methyl ether (CPME), glycerol, dimethyl isosorbide (DMI), γ-valerolactone (GVL) and Cyrene are some of the most common examples, which can be also defined as bio-derived solvents. Furthermore, other types of compounds are also commonly employed as green solvents, i.e., organic carbonates (OCs), CO₂ and supercritical CO₂ (scCO₂), ionic liquids (ILs) derived from amino acids, proteins, lignin and polysaccharides,¹⁶ deep eutectic solvents (DES) and natural DES.^17–19

Among them, this review will focus on OCs, exploring their use as media in different fields.

These compounds offer a broad range of proprieties, which are tunable according to their chemical structures. In the literature, numerous organic carbonates, both commercially available and custom-made, have been employed in various fields, as illustrated in Fig. 1 (OC applications) and Fig. 2 (most used OCs). According to our extensive literature screening covering the last 40 years, OCs have been mostly investigated as electrolyte solvents, media in organic synthesis and for the extraction of compounds from different biological and non-biological matrices.

Fig. 1 Literature screening on the applications of OCs as solvents. The bibliographic search was conducted exploiting the Reaxys database choosing years from 1980 up to July 2024, with the selected keywords “solvent” and “carbonate” combined with the OC chemical structure considering any side chain group and ring-closure. According to this screening, 2761 articles and patents were obtained, among which works in which OCs were used as reagents or solvents and reagents were excluded.

Fig. 2 Literature screening on the OCs used as solvents. The bibliographic search was conducted exploiting the Reaxys database choosing years from 1980 up to July 2024, with the selected keywords “solvent” and “carbonate” combined with the OC chemical structure considering any side chain group and ring-closure. According to this screening, 2761 articles were obtained, among which works where OCs were used as reagents or solvents and reagents were excluded.

Nevertheless, OCs have found applications in several other fields ranging from analytical chemistry, principally as mobile phases for the separation and identification of products, to the biological/biochemical area and for the restoration of ancient artifacts (Fig. 1). Most of the OCs used are dialkyl carbonates (DACs), which can be easily purchased on the market at a low cost, i.e., dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC) and ethylene carbonate (EC) (Fig. 2). It must be mentioned that PC and EC are well-known electrolyte solvents, which represent the most studied application area for OCs (Fig. 1). Despite this predominance, custom-made OCs have also been employed in different areas to meet polarity or solubility criteria required for specific applications (Fig. 2).

Based on this premise, the present work aims to present an overview focused exclusively on the applications of OCs as solvents, highlighting their use in lab-scale chemical transformations, large-scale industrial processes and end-of-use products. Numerous reviews have been published on OCs as green reagents. However, to the best of our knowledge, this is the first comprehensive review solely focusing on their use as green media.

In particular, the rationale of this work has been organized as follows:

2. Properties and stability of organic carbonates

OCs display completely different proprieties depending on their chemical structure. The characteristics of the most studied OCs (Fig. 1 and 2), DMC, DEC, EC and PC, together with some of the most employed traditional toxic media (see also Table 2) are reported in Table 1.

Table 1 Physico-chemical proprieties of the most investigated organic carbonates compared with some of the most employed toxic solvents

	DMC	DEC	EC	PC	CH2Cl2	CH3CN	Toluene	DMF
LEL: lower explosive limit; UEL: upper explosive limit; n.r.: information not reported, V = volume.a Values available in Sigma-Merck safety data sheet (SDS) of the corresponding compound.b Values available at https://pubchem.ncbi.nlm.nih.gov/.c Values available at https://depts.washington.edu/eooptic/linkfiles/dielectric_chart%5B1%5D.pdf.
Molecular weight (g mol^−1)	90.08	118.13	88.06	102.09	84.93	41.05	92.14	73.09
Melting point (°C)	4.6^20	−43^20	34–37^21	−48.8^3	−97^a	−48^a	−93^a	−61^a
Boiling point (°C)	90.3^20	126^20	248^22	240^3	40^a	81^a	110^a	153^a
Density (g cm^−3)	1.069^20	0.975^20	1.321^23	1.201^3	1.325^a	0.786^a	0.865^a	0.944^a
Water solubility (g L^−1)	139^20	Insoluble^20	778^24	200^24	0.013^b	>800^b	0.53^b	1000^b
Dielectric constant (ε)	3.20^25	2.82^26	89.78^27	66.6^28	8.93^c	37.5^c	2.38^c	36.7^c
Dipole moment (μ, D)	0.91^29	1.07^30	4.81^27	5.36^28	1.55^c	3.45^c	0.43^c	3.86^c
Explosion limit^a
LEL (% V)	4.2	1.4	3.6	1.8	13.0	4.4	1.2	2.2
UEL (% V)	12.9	11.0	16.1	14.3	22.0	16.0	7.1	16.0
Flash point^a
Closed cup (°C)	16.0	25.0	143	132	Does not flash	2.0	4.4	57.5
Ignition temperature^a (°C)	n.r.	445	n.r.	n.r.	605	n.r.	n.r.	435
Vapour pressure^a (hPa at 20.0–25.0 °C)	24	13	<1	0.06	584	98.64	30.88	3.77
Solvent polarity (ET(30), kcal mol^−1)	41.1^31	36.2^31	48.6^32	46.6^31	40.7^31	45.6^31	33.9^31	43.2^31

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Table 2 OCs employed as green solvents in organic synthesis as substitutes for toxic or hazardous solvents

General application	Specific application	Organic carbonate solvents	Toxic solvents	Ref.
n.r.: information not reported; DMA: dimethyl acetamide, GPC: glycerol carbonate propionate, GCB: glycerol carbonate butyrate, GC: glycerol carbonate, DPC: dipropyl carbonate, BC: butylene carbonate, Gly2C: bis(2-methoxyethyl) carbonate, GlyMC: 2-methoxyethyl methyl carbonate, DGlyMC: 2-(2-methoxyethoxy)ethyl methyl carbonate, DGly2C: bis(2-(2-methoxyethoxy)ethyl) carbonate, DPhC: diphenyl carbonate, EMC: ethyl methyl carbonate, DAllC: diallyl carbonate.
Simple chemical reactions	Etherification	PC	CH2Cl2, CH3CN, benzene, toluene	88 and 91
	Esterification	DMC	n.r.	87
	Chlorination and bromination	DMC, PC, DEC	CHCl3, chlorobenzene, CCl4	89 and 90
	Oxidation and epoxidation	DMC, DEC, PC, DPC, BC	CH3CN, ionic liquids, DMF, NMF, NMP, DMA, THF	93–104
	Amine synthesis	DMC, PC	CHCl3, Toluene	105–107
	Amide synthesis	DMC	CH2Cl2	108
	Wolff rearrangement/acylation	DMC, DEC	DMF, CH3CN, toluene, DMSO, DCE	109
	Dehydration	DMC	THF	110–116
Rh-catalysed reactions	Hydroformylation	DMC, DEC, PC	Toluene, benzene	117–120
	Co-oligomerization	PC	n.r.	117
	ortho-Diarylation	DEC	NMP, 1,4-dioxane	121
	Hydroacylation	PC	DCE	122
Pd-catalysed reactions	Asymmetric allylic substitution	PC, BC, DEC	CH2Cl2	123
	Telomerization	DMC, DEC, EC, PC, BC, GCP, GCB	CH3CN	78
	Allylation of heteroarenes	DMC	DMF, 1,4-dioxane, CH3CN	124
	Synthesis of lactones	DMC	Toluene, CH2Cl2	125
	Hydrogenation	DMC	n-Heptane	126
	Phenoxycarbonylation of aryl iodides	PC, EC	DMF, 1,4-dioxane	127
	Coupling	DMC, DEC, EC, PC, GC	THF, toluene, anisole, 1,4 dioxane, DMA, DMF	128–134
	Synthesis of oxime ether derivatives	DMC	n.r.	135
Ni-catalysed reactions	Hydrodeacetoxylation	DMC	Toluene	136
Pt-catalysed reactions	Hydrosilylation	PC	Toluene, cyclohexane	137 and 138
Ru-catalysed reactions	Olefin metathesis	DMC, PC	Benzene, toluene, CH2Cl2, chlorobenzene	139–142
Other applications as media in organic synthesis	Organic carbonates and ionic liquids as media in organic synthesis	DEC, PC	n.r.	143–145
	Phase transfer catalysis	DMC	Toluene, chlorobenzene	146
	Enantioselective reactions	PC, EC	DMF, CH2Cl2	147–151
	Photocatalytic reactions	DMC	Toluene, CH3CN, BTF, DMF, benzonitrile, propionitrile, butyronitrile	152–158
Other reactions	Condensation/rehydration	DMC	cyclohexane	159
	Radziszewski reaction	PC	DMSO, DMF	160
	Synthesis of cyclodextrin-based supramolecular assemblies	DEC	n.r.	161
	Complexation	PC	DMF	162
	Claisen rearrangement	PC	DCB	163
	Ring opening	DMC	CH2Cl2, Et2O, CH3CN	164

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Generally, cyclic OCs display a higher dipole moment and dielectric constant compared to linear OCs. Therefore, PC in particular is well-suited for anhydrous electrochemical applications.^33,34 Moreover, the polarity and hydrogen-bond acceptor properties (basicity, β) of PC (0.39) match perfectly with that of acetonitrile (0.38).³⁵ Linear DACs such as DMC and DEC, although displaying similar basicity, possess lower polarities, which resemble methylene chloride and THF.^36–39 Only scant data are available for other organic carbonates even if modelling predictions of these parameters may be a powerful tool to overcome this limitation.^40–44

Concerning the solubility of OCs, most of them only show limited or no miscibility with water,^45,46 despite displaying characteristics of highly dipolar solvents similar to other compounds such as dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF).⁴⁶ In a recent study, it was demonstrated that the substitution of hydrocarbon chains with more polar glycol-based moieties led to a drastic increase in the water solubility of OCs.^24,47 Thus, the tuning of the side chains of OCs may allow the wider application of these compounds both as solvents and reagents.^47,48

OCs can be considered chemically stable under normal conditions. However, at elevated temperature, these compounds can decompose, releasing mainly CO₂. In particular, DMC can release CO₂ and dimethyl ether at T > 150 °C in an inert atmosphere, while methanol can originate from DMC hydrolysis in the presence of water.⁴⁹ Similarly, DEC can decompose into ethylene, ethanol and CO₂.⁴⁹ Also, longer chain DACs have been shown to decarboxylate in the presence of hydrotalcites, producing the corresponding ethers.⁵⁰ In general, linear OCs degrade at lower temperatures than cyclic OCs, i.e., EC degrades at 335 °C, whereas PC at 316 °C.⁴⁹

It should be mentioned that the reactivity of DMC and its derivatives was thoroughly investigated in the work of Tundo et al., according to which it is evident that these compounds can easily react with a variety of nucleophiles, yielding either the corresponding alkoxycarbonylated or alkylated derivatives according to the reaction conditions.⁵¹

Therefore, the proprieties of OCs as ambident electrophiles may hamper their applications as media, with possible side reaction occurring due to their reactivity. Similarly, cyclic OCs may undergo ring opening in the presence of a suitable nucleophile, thus leading to the formation of side products. Some examples of these issues are reported throughout section 4.

3. Global market, production costs and safety aspects of organic carbonates

3.1 Global market production of the principal organic carbonates

According to ChemAnalyst and KBV reports, the global EC production was estimated to be between 320 000 and 460 000 tonnes in 2022 with a projection to reach 865 000 tonnes by 2032 (compound annual growth rate (CAGR) of 6.5% from 2023 to 2032).^52,53 Different reports forecasted the global EC market size to reach a value between 970.4 million USD and 1.16 billion USD by 2030, with a CAGR from 8.6% to 13.7% during the forecast period.^53,54

The global market of PC was approximately 470 000 t per year in 2022, which is anticipated to grow at a CAGR of 5.6% until 2032, reaching 800 000 t per year (ChemAnalyst report). The increasing demand for electric vehicles and portable electronic devices is also driving the PC market, together with its utilization in skincare formulation products, coatings, paints, sealants, adhesives and degreasers.^55,56

According to a report by Grand View Research, the global PC market was valued at approximately 393.1 million USD in 2023, which is projected to reach 610.9 million USD by 2030.⁵⁶

The global DMC production is the highest among the commercially available OCs, with a value estimated around 926 000 tonnes in 2022 and an expected CAGR of 5.4% until 2032,⁵⁷ with its major application being polycarbonate production.⁵⁸ The DMC market was valued between 1.10 and 1.17 billion USD in 2023, which is projected to reach 1.9 billion USD by 2028.⁵⁹

3.2 Techno-economic analysis of organic carbonate production

One of the most used processes for the production of DMC, patented by Asahi Kasei in 2006, involves CO₂ insertion into epoxides, with the formation of EC or PC as intermediates. Subsequently, they are converted to DMC via a transesterification reaction with methanol.^60,61 Other well-known procedures for the production of rely on the oxidative carbonylation of methanol (EniChem, Bayer and UBE processes)^62–65 and on the alcoholysis of urea.^66,67

In this aspect, various techno-economic assessments were performed over the years to evaluate the economic feasibility of DMC production through different routes, mainly involving CO₂ as the starting reagent.^68–70 Considering the oxidative carbonylation of methanol and direct methanolysis of urea as synthetic methods, the steps of methanol and urea syntheses appear to be the major capital investment contributors, rather than the DMC synthesis step.⁷⁰ In this scenario, the DMC production cost was calculated to be around 520 € per t.⁶⁸

The Asahi Kasei route was found to give the best performance in terms of energy consumption (11.4% improvement), net CO₂ emission (13.4% improvement), global warming potential (58.6% improvement) and human toxicity-carcinogenic effects (99.9% improvement) compared to the Bayer process.⁶⁹ It is worth mentioning that in the process forming EC as an intermediate to DMC, high-purity ethylene glycol (EG) is also produced as a by-product.⁶⁹ EG can then be employed in numerous other industrial processes, such as in the synthesis of polyethylene terephthalate (PET) and polyethylene furanoate (PEF) as well as for energy, automobile, and chemical applications.

In addition, the techno-economic assessment performed by Kontou and co-workers in 2022 analysed the DMC/CO₂ ratio of different DMC production concepts based on the initial formation of EC from the reaction of ethylene oxide (EO) with CO₂, followed by its transesterification with methanol to produce DMC and EG as side products.⁷¹

Syntheses carried out with fossil-derived methanol from the market and CO₂ procured from a pipeline network were compared to that in which MeOH was produced on-site using externally procured green hydrogen and CO₂ was captured from a coal-fired power plant. The DMC/CO₂ ratio of the scenarios considered ranged from 1.38 kg kg⁻¹ to 0.53 kg kg⁻¹, which can be further lowered to negative CO₂ emission values (−105.48 kt a⁻¹) when grid electricity and natural gas are used for covering the electricity and heating needs of the plant.⁷¹

According to these evaluations, the DMC minimum selling price of the different scenarios ranged from 634 to 1263 € per t, which could be reduced (659–707 € per t) assuming a future decrease in the price of green hydrogen. In this case, the minimum cost of DMC would range between 659 and 707 € per t, which is below the current market price of 849 € per t.⁷¹

Concerning the other most used cyclic OCs, i.e., EC and PC, they can be obtained using the same procedures previously described for the synthesis of DMC, given that they are formed as intermediates from the reaction of CO₂ with the corresponding epoxide (namely, EO and propylene oxide (PO)). Consequently, it is safe to assume that their production cost and CO₂ emissions would be lower compared to DMC.

Despite this consideration, other studies focused on the techno-economic analysis of alternative EC and PC syntheses, either starting from EG instead of the petroleum-derived EO⁷³ or from CO₂ and PO in the presence of different ILs as catalysts (namely, [P66614][Br] and 1-n-ethyl-3-methylimidazolium chloride), respectively.^74,75 In the case of the synthesis of PC, the optimal configuration for the former system displayed an energy consumption of approximately 0.6 kW h kg_PC⁻¹ and utility costs of 6.6 USD per t_PC.⁷⁴ Alternatively, in the latter case, the net cost of duty was calculated to be 4.26 USD per t_PC considering the production of 91 000 t per year of PC using 4.5 t h⁻¹ of CO₂.⁷⁵

In the production of EC, none of the cases tested were shown to be feasible for commercialization at an annual EC production of 5 ktonnes. The minimum selling price of EC would be in the range of 6.44 USD per kg to 16.73 USD per kg against the current market price fluctuating between 0.88 and 1.16 USD per kg.^73,76

Data about the market production and costs of other more complex organic carbonates are still lacking. However, various processes for the synthesis of linear OCs rely on the use of DMC as the starting reagent, which is then subjected to transesterification in the presence of the desired alcohol.^24,77 The custom-made cyclic OCs reported in this review were instead synthesized either by reacting GC with the corresponding acyl chloride⁷⁸ or by reacting a suitable triol with urea in the presence of a catalyst.⁷⁹

3.3 Safety aspects of organic carbonates

Organic carbonates are generally considered non-toxic compounds, with most of the toxicological studies performed on DMC. DEC is listed as “an experimental tumorigen and teratogen” and “mildly toxic by subcutaneous route”. Specific toxicity data obtained through animal testing were collected by Pacheco and co-workers.⁸⁰

A safety assessment regarding DACs used in cosmetics, namely, dicaprylyl carbonate, bis-propylheptyl carbonate, C₁₄–C₁₅ dialkyl carbonate, diethylhexyl carbonate, DMC and DPC, was published by The Cosmetic Ingredient Review (CIR) Expert Panel established with the support of the U.S. Food and Drug Administration (FDA) and the Consumer Federation of America.^72,81 This report presented an overview of the use and toxicokinetic and toxicological effects of the studied DACs with experiments conducted on rats, cavies and human skin samples, concluding that the studied DACs “are safe in the present practices of use and concentration […] when formulated to be non-irritating”.⁸¹

The Environmental Protection Agency (EPA) indicated PC as a low concern chemical based on experimental and modelled data.⁸³ Acute toxicity tests were performed by dermally administering PC to rats and rabbits at 5000 mg per kg-bw and 3000 mg per kg-bw, and no mortality was seen after 14 days (LD₅₀ > 5000 and LD₅₀ > 3000), respectively. Rats were also exposed to PC aerosol via inhalation at 0.1, 0.5 and 1.0 mg L⁻¹ for 6 h day⁻¹, 5 days per week, for 14 weeks. Ocular irritation and periocular swelling were seen at 0.5 and 1.0 mg L⁻¹. Alternatively, the rats exposed to PC did not develop any chromosomal aberrations after intraperitoneal injection of PC at 1666 mg per kg-bw.⁸⁴

In addition, cytotoxicity tests were conducted via the colorimetric MTT assay on a selection of custom-made alkyl methyl carbonates and 2-(2-methoxyethoxy) carbonates, (DGly)₂C and DGlyMC, respectively. None of them showed any cytotoxicity effect at all the tested concentrations, both after 24 h and 48 h after the treatment of the cells. Moreover, computational analyses employing different software (CASE Ultra by MultiCASE Inc., USA; Model Applier by LeadScope, USA) and models based on quantitative structure–activity relationships (QSAR) predicted that all the tested DACs were not mutagenic, in compliance with ICH guideline M7.^24,82

4. Organic carbonates as media in organic syntheses

OCs have been broadly investigated as green reaction media for many chemical transformations. In 1942, Wallingfod, Thorpe and Homeyer firstly reported DACs as solvents in the alkylation of malonic esters, β-keto esters and α-cyano esters (Scheme 1).⁸⁵ They discovered that using DACs as media, the formation of the sodium derivative of these substrates went to completion and cleavage by alcoholysis was avoided. Several malonic esters, not achievable by the usual methods, were prepared operating in DEC solution. For instance, alkyl chains such as Et, Bu, iso-amil, n-amyl, allyl, benzyl, and sec-butyl were introduced with yields ranging from 70% to 95% (Scheme 1).⁸⁵

Scheme 1 (a) First examples of organic carbonates as reaction media–alkylation of malonic esters in DEC and (b) alkylation of β-keto and α-cyano esters in organic carbonates.⁸⁶

Since the 1960s, the application of OCs as solvents has spread to nearly every field of chemistry.⁴⁶ Moreover, cyclic carbonates, especially EC and PC, are well known for their high solvency.⁸⁶ Thus, organic cyclic and linear carbonates started gaining attention given that they might partially or totally replace more expensive or more toxic solvents such as N-methyl pyrrolidone (NMP), dichloromethane, DMF, and isophorone⁴⁶ in various synthetic approaches (Table 2 and Fig. 3).

Fig. 3 Chemical structures of cyclic and acyclic organic carbonates that have applications as reaction media.

Linear and cyclic carbonates have been widely used as green solvents due to their non-hazardous nature, replacing the more toxic and fossil-derived compounds normally used in different organic synthesis processes.

In many cases, OCs have been shown to be viable alternative solvents that can compete, and in some cases, even outperform traditional solvents. In the following sections, we present some of the most prominent works where cyclic and linear OCs were used as solvents in different organic synthesis reactions, as summarized in Table 2.

4.1 Etherification and esterification reactions

To the best of our knowledge, only one example was reported in the literature employing OCs as solvents in esterification reactions. In this study, the synthesis of lipophilic esters of tyrosol, homovanillyl alcohol and hydroxytyrosol was performed in DMC. The reactions were carried out at room temperature in the presence of the selected C2–C18 acyl chloride added in slight excess. The final products were isolated in yields in the range of 90% to 98% in the case of tyrosyl and homovanillyl-derived esters, while yields of 60% to 68% for hydroxytyrosyl esters.⁸⁷

Similarly, only scant works focused on the application of OCs as solvents in etherification reactions. In particular, the symmetrical and non-symmetrical etherification of benzyl alcohols was performed in PC, replacing CH₂Cl₂ and CH₃CN. The symmetrical etherification reaction was carried out in the presence of FeCl₃·6H₂O (5 mol%) as the catalyst and led to the corresponding symmetrical ethers in 53% to 91% yields.⁹¹ Recently, DMC was employed to replace benzene and toluene in the self-etherification of the bio-based platform chemical 5-hydroxymethyl furfural (HMF) to obtain 5,5′-[oxybis(methylene)]bis-2-furfural (OBMF). The reaction was carried out in the presence of a heterogeneous Lewis acidic catalyst, Fe₂(SO₄)₃, allowing the recovery of OBMF in ca. 80% yield.⁸⁸

4.2 Chlorination and bromination

Appel chlorination and bromination mediated by triphenylphosphine oxide (PPh₃O) were performed using DMC as the solvent instead of chloroform (Scheme 2).⁸⁹ The Appel reaction allows the conversion of alcohols to the respective activated alkyl halide promoted by PPh₃O. Triphenylphosphine oxide is converted to its respective chlorophosphonium salt (CPS) by reaction with oxalyl chloride (COCl)₂. Finally, CPS reacts with an alcohol, leading to the corresponding alkyl chloride.⁸⁹

Scheme 2 Appel chlorination and bromination reactions of different alcohols in DMC.⁸⁹

The substitution of DMC with chloroform led to a slightly longer reaction time (15 min instead of 5 min) to achieve the total conversion of benzyl alcohol into its chloride. This suggests that the generation of CPS in DMC is a slower process than in chloroform. In addition, CPS needed a higher amount of DMC to be completely dissolved.⁸⁹ The isolated yield values for the chlorination and bromination reactions of different alcohols in DMC varied between 21% and 83% in the former case, and 43% to 89% in the latter case.⁸⁹

Another example is the Wohl–Ziegler bromination of 2-cyano-4′-methylbiphenyl conducted in PC (conversion and yield of 83% and 76%, respectively) and DEC (conversion and yield of 89% and 71%, respectively), replacing the commonly employed chlorinated solvents such as chlorobenzene and carbon tetrachloride. The obtained product, 4′-(bromomethyl)-2-cyanobiphenyl (BCB), is a key building block to various sartans, which are valuable nonpeptide angiotensin II antagonists (Scheme 3).⁹⁰

Scheme 3 Bromination of 2-cyano-4′-methylbiphenyl using N-bromosuccinimide (NBS) to yield 4′-(bromomethyl)-2-cyanobiphenyl (BCB).⁹⁰

4.3 Oxidation reactions

DACs were investigated as alternative green solvents for the oxidation of aryl–alkyl ketones¹⁰¹ and various aromatic compounds, i.e., styrene, naphthalene derivatives, sulfides, alcohols and phenolic molecules, in the presence of different catalysts.^93,96,97 Bernini and co-workers relied on a H₂O₂/methyltrioxorhenium (MeReO₃, MTO) catalytic system using DMC as the medium. The studied oxidations proceeded with good conversions (>98% via GC-MS) and yields of up to 98%.⁹²

DMC showed good performances as a green medium for the chemoselective and regioselective oxidation and demethylation of phenolic compounds in the presence of polymer-supported 2-iodoxybenzoic acid (IBX) to obtain bioactive catechol derivatives (Scheme 4A).^93,96 DMC was also applied for the oxidation of aromatic alcohols to the corresponding carbonyl compounds employing zinc peroxide (ZnO₂) nanoparticles (Scheme 4B; yields varying from 79% to 98%).⁹⁷

Scheme 4 (A) Chemoselective and regioselective oxidation of phenolic compounds in the presence of polymer-supported IBX⁹³ and (B) oxidation of aromatic alcohols to the corresponding carbonyl compounds in DMC.⁹⁷

DMC was utilized as a solvent for the epoxidation of alkenes (Scheme 5) in substitution of the commonly employed acetonitrile. The reactions were performed in the presence of different heterogeneous catalysts, i.e., [PO₄{WO(O₂)₂}₄] (PW₄), nitrogen-free or nitrogen-doped carbon nanotubes (CNTs or N-CNTs)¹⁰² and silica-supported cobalt-based (Co/SiO₂) materials.⁹⁴

Scheme 5 (A) Cyclooctene (CyO) epoxidation with H₂O₂ in DMC and (B) epoxidation of bio-renewable terpenes in DMC.⁹⁴

In particular, cyclooctene (CyO) epoxidation with H₂O₂ in DMC showed better performances in the presence of PW₄/CNTs and a tetrahexylammonium salt of PW₄ (THA-PW₄) as catalysts (conversion: 93% and 80; epoxide selectivity: 97% and 100%, respectively) compared to when PW₄/N-CNTs was employed (conversion: 37%; epoxide selectivity: 89%) despite similar initial reaction rates (Scheme 5A).¹⁰² Encouraging results were also achieved for the epoxidation of a series of bio-renewable terpenes in DMC, i.e., β-pinene, camphene, 3-carene, limonene, valencene and β-caryophyllene (yield varying between 46% and 99%) as well as terpenes containing an alcohol functionality, i.e., myrtenol, nopol, (S)-(−)-perillyl alcohol and linalool (yield varying between 45% and 92%) using molecular oxygen, isobutyraldehyde (IBA) as a sacrificial reductant and a Co/SiO₂ catalyst (Scheme 5B).⁹⁴

In addition, the catalytic performance of PW₄/CNT catalysts was assessed in the selective oxidation of organic sulfides with H₂O₂ using methyl phenyl sulfide (MPS) as the model substrate (Scheme 6) and compared with that of homogeneous PW₄. In this case, the reactions carried out in acetonitrile in the presence of homogeneous THA-PW₄ showed a higher sulfide conversion (93%) and selectivity to sulfoxide (83%) compared to that employing DMC (86% and 70%, respectively).¹⁰²

Scheme 6 Oxidation of organic sulfides in DMC and acetonitrile as media in the presence of H₂O₂ and PW₄/CNTs as the catalyst.¹⁰²

Synthetic protocols for the synthesis of guanidines and amides using DMC as a green medium were reported in the studies by Baeten and Ramarao, respectively. Particularly, guanidines can be obtained via the oxidative rearrangement of amidines into carbodiimides, followed by an in situ reaction with amines (Scheme 7A).¹⁰⁴ Amides can be isolated from the corresponding imines using molecular oxygen in air as the sole oxidant (Scheme 7B).¹⁰³

Scheme 7 DMC as the solvent for the (A) synthesis of guanidines from amidines and (B) synthesis of amides from imines. NHC: N-heterocyclic carbene.^103,104

PC was found to significantly enhance the oxidation reaction of cyclohexane over the Au/SiO₂ catalyst with 22% conversion and 83% selectivity towards a cyclohexanone/cyclohexanol mixture (K/A-oil; 65% and 18%, respectively), which can be used for the production of Nylon-6 and Nylon-6,6.⁹⁸ The conversions (18% to 22%) and selectivity (about 81%) using the cyclic carbonates towards K/A-oil were much higher than that of linear organic carbonates, i.e., DMC, DEC, DPC, EC and BC (conversions between 3% and 5%; selectivity between 44% and 56%).⁹⁸

Another relevant example is the iron-catalysed aerobic oxidation of 2-benzylpyridines to their corresponding ketones, which was performed in continuous flow using PC instead of more toxic dipolar aprotic solvents, i.e., CH₃CN, DMF, NMF, NMP, DMA and DMSO (Scheme 8).⁹⁹ The reaction time was significantly reduced from hours to minutes and molecular oxygen was replaced by synthetic air as the oxygen source.⁹⁹

Scheme 8 Iron-catalysed aerobic oxidation of 2-benzylpyridines in continuous flow using PC as the solvent.⁹⁹

4.4 Synthesis of amines and amides

DACs were demonstrated to be suitable reaction media for the synthesis of both linear and cyclic amines. For example, primary amines were obtained via the Delépine reaction¹⁶⁵ (Scheme 9) by reacting hexamethylenetetramine (HMTA) with an alkyl or benzyl halide in the presence of DMC instead of the commonly employed solvent CHCl₃. The product was obtained in comparable yields.¹⁰⁵

Scheme 9 Synthesis of primary amines via the Delépine reaction.¹⁰⁵

Moreover, DMC was used as the solvent for the synthesis of several pharmaceutically relevant building blocks, i.e., N-Boc-3-pyrroline, with a yield similar to the previously reported synthetic procedures (86% vs. 84.9%).¹⁰⁵

DMC also displayed encouraging results as a solvent replacing 1,4-dioxane and toluene for the iron-catalysed one-pot hydrosilylation reaction of a wide range of N-alkylated and arylated cyclic amine derivatives including the pharmaceuticals fenpiprane and prozapine (Scheme 10). The test reactions conducted with glutaric acid, aniline and DMC under visible light irradiation showed similar yield values to that performed using 1,4-dioxane and toluene (70%, 75% and 72% yield, respectively).¹⁰⁶ Moreover, the use of Fe(OTf)₂ as an additive in some cases further increased the reaction yield of the desired cyclic amines up to 96%.¹⁰⁶

Scheme 10 Synthesis of N-substituted cyclic amines using DMC as the solvent.¹⁰⁶

α-Substituted homoallylamines can be obtained using DMC and PC as solvents via the cationic 2-aza-Cope rearrangement of aldimines generated in situ via the condensation of commercially available aldehydes and 1,1-diphenylhomoallylamines (81–98% product yield).¹⁰⁷

DMC was also employed as a green substitute for dichloromethane in the microwave-assisted synthesis of peptidomimetic arylamides, compounds that can inhibit cysteine and serine-like proteases.¹⁰⁸ Overall, the yields obtained with the use of DMC (32–47%) were slightly lower compared to that obtained when CH₂Cl₂ was used as the solvent (44–70%), regardless of the coupling reagent employed (Scheme 11). Nevertheless, the isolation of the compounds when the reaction was performed in CH₂Cl₂ was hampered due to the enhanced solubility of the byproducts in this solvent.¹⁰⁸

Scheme 11 Microwave-assisted synthesis of peptidomimetic arylamides in DMC. COMU: third generation uronium-type coupling reagent [(1-cyano-2-ethoxy-2-oxoethylidenaminooxy) dimethylamino-morpholino carbenium hexafluorophosphate].¹⁰⁸

4.5 Wolff rearrangement/acylation reaction

DEC was employed as a green solvent for the chemoselective cascade Wolff rearrangement/acylation reaction between 5-aminopyrazoles and diazo compounds (Scheme 12).¹⁰⁹ Among the different solvents tested, i.e., DCE, DMF, CH₃CN, dioxane, DMA, EtOH, tBuOH, BuOH, toluene, DMC and DMSO, carbonate media seemed to be particularly beneficial for in this reaction, with DEC and DMC giving yields of up to 95% and 70%, respectively.¹⁰⁹

Scheme 12 Wolff rearrangement/acylation reaction between 5-aminopyrazoles and diazo compounds.¹⁰⁹

4.6 Dehydration reaction: synthesis of 5-(hydroxymethyl)furfural

DACs such as DMC, DEC, PC and diallyl carbonate (DAllC) have been tested as co-solvents in several synthetic approaches to 5-(hydroxymethyl)furfural (HMF), a well-known bio-based platform chemical, starting from D-fructose or D-glucose (Table 3). DMC was used in the reaction mixture as the extraction solvent for HMF; its use was found to reduce the formation of humins and numerous byproducts (#1, Table 3).^111,112

Table 3 Organic carbonates as media for the synthesis of HMF from D-fructose

#	Sugar	Solvent	Catalyst	T (°C)	t (h)	Conv. (%)	Selectivity HMF (%)	Yield HMF (%)	Ref.
n.r.: value not reported; n.d. compound not detected.
1	D-Fructose	DMC/H2O	CeP3 (35 wt%)	150	6	73	93	68	111
		DEC/H2O				49	88	45
		PC/H2O				46	85	40
		DAllC/H2O				43	80	36
2	D-Glucose	DMC/EMIMBr	SnCl4 (10 mol%)	100	2	n.r.	n.r.	58	112
3	D-Fructose	DMC/TEAB	Amberlyst-15 (10 wt%)	90	5	99	n.r.	77	114
		DMC/TEAB	Purolite CT275DR (5 wt%)	110	2	n.r.	98	73	116
4	Corn-cob	DMC	AlCl3 (30 wt%)/HCl (4 N)	180	6	n.r.	n.r.	35	113
	Sugarcane bagasse					n.r.	n.r.	60
	Rice-straw					n.r.	n.r.	37
	Corn-straw					n.r.	n.r.	47
5	D-Glucose	DMC	Sulfonated graphitic carbon nitride (S-GCN, 10–50 wt%)	200	5	n.r.	99	23	115
	D-Fructose			200	5	n.r.	99	17
	Cellobiose			200	5	n.r.	99	16
	Sucrose			200	5	n.r.	99	30
	Starch			200	5	n.d.	n.d.	n.d.

---

DMC was also employed as the main reaction medium to achieve HMF either from D-fructose (#3, Table 3)^114,116 or from more complex mixtures, i.e., cellobiose, sucrose, starch, corn-cob, sugarcane bagasse, rice-straw and corn-straw (#4 and 5, Table 3) even if in the latter cases with lower HMF yields.^113,115 The reason for the utilization of DMC as the medium for sugar dehydration into furan-based molecules may be the enhanced stabilization capacity of compounds containing a carbonyl moiety, i.e., methyl isobutyl ketone (MIBK), OCs and DMF towards furanics.^166,167 On this topic, a comprehensive study on the stability of different furan-based compounds both in acidic and basic media in the presence of various solvents was recently carried out by Ananikov and co-workers.¹⁶⁶

4.7 Rh-catalysed reactions

The Rh-catalysed hydroformylation (oxo synthesis) of caryophyllene oxide and β-caryophyllene was carried out employing DMC and DEC among other green solvents, replacing the conventionally used hydrocarbons such as toluene and benzene (Scheme 13A).¹¹⁹ The reactions showed high selectivity and complete substrate conversion despite a slightly lower reaction rate than the procedure conducted in toluene, whereas p-cymene performed with the same efficiency.¹¹⁹

Scheme 13 (A) Hydroformylation of caryophyllene oxide and β-caryophyllene.¹¹⁹ (B) Isomerizing hydroformylation of trans-4-octene to n-nonanal in a two-phase catalytic reaction system.¹¹⁸ (C) Rh-catalysed hydroformylation of higher olefins (C > 6), with a mixture of PC and n-heptane as the solvent system.¹²⁰ (D) Rh-catalysed co-oligomerization of fatty acid derivatives.¹¹⁷ (E) Rh-catalysed ortho-diarylation of various arylheteroaryl substrates with N-ligand employing DEC as the green solvent.¹²¹ (F) Intermolecular alkyne hydroacylations using PC as the solvent.¹²²

Another suitable solvent for regioselective, Rh-catalysed hydroformylation reactions is PC, which was shown to effectively mediate the isomerizing hydroformylation of trans-4-octene to n-nonanal in a two-phase catalytic reaction system (Scheme 13B). PC could increase the catalyst activity, leading to 95% conversion and up to 95% selectivity for the linear aldehyde.^117,118 Alternatively, tests performed employing PC/dodecane and PC/dodecane/p-xylene solvent mixtures showed that the higher the PC concentration, the higher the selectivity of n-nonanal. This significant influence of PC on the selectivity can be explained by the electron-withdrawing effect of the carbonate group, which may be able to interact with the β-hydride atoms of the σ-rhodium-complex, leading to faster isomerization.¹¹⁸

Similar results were achieved by Tijani and co-workers in the Rh-catalysed hydroformylation of higher olefins (C > 6), where a mixture of PC and n-heptane was reported as the most suitable solvent system (Scheme 13C).¹²⁰

A solvent mixture of PC/conjugated sunflower fatty acid methyl ester (SFAME)/1,4-dioxane was successfully employed in the Rh-catalysed co-oligomerization of fatty acid derivatives with ethylene, leading to the formation of internal branched fatty substances (Scheme 13D).¹¹⁷ The total yield of the process be increased to 98% in this solvent system under mild conditions (70 °C, 3.0 MPa) and the turnover frequency was enhanced by a factor of 100 (2 vs. 220 h⁻¹).¹¹⁷

In addition, the selective ortho-diarylation of various arylheteroaryl substrates could be achieved via the N-ligand directed Rh-catalysed coupling of highly functionalized aryl phenolate derivatives employing DEC as a green solvent to replace NMP and 1,4 dioxane (Scheme 13E).¹²¹ Overall, using DEC as the medium yielded the desired products even with bulkier, more hindered reagents as well as with electron-donating substituents in the para-, meta- and ortho-position.¹²¹

Finally, PC was employed by Lenden et al. as a green solvent for intermolecular alkyne hydroacylations, behaving as a valid alternative to DCE and acetone (Scheme 13F).¹²² The results showed that these reactions could be carried out in PC using [Rh(nbd)₂]BF₄ as the catalyst in combination with 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, obtaining yields in the range of 73% to 95%.¹²²

4.8 Pd-catalysed reactions

Linear and cyclic OCs were also shown to be viable alternatives to chlorinated solvents in Pd-catalysed transformations. For example, PC, BC, and DEC were tested as substitutes for CH₂Cl₂ in the Pd-catalysed asymmetric allylic substitution reactions of rac-1,3-diphenyl-3-acetoxy-prop-1-ene with dimethyl malonate or benzylamine as nucleophiles (enantioselectivities ranging from 83% to 98%, Scheme 14). The use of these green solvents in several cases led to enhanced yields and enantioselectivities compared to CH₂Cl₂.¹²³

Scheme 14 Pd-catalysed asymmetric allylic alkylation of rac-1,3-diphenyl-3-acetoxy-prop-1-ene with dimethyl malonate or benzylamine using DACs as green solvents.¹²³

Behr et al. investigated the substitution of CH₃CN as the solvent with different linear DACs (DMC and DEC), cyclic DACs (EC, PC and BC), custom-made glycerol carbonate esters (glycerol carbonate propionate (GCP) and glycerol carbonate butyrate (GCB)) as well as DAC mixtures in the Pd-catalysed telomerisation of butadiene with carbon dioxide, leading to the formation of δ-lactone 2-ethylidene-6-heptene-5-olide (Scheme 15).⁷⁸

Scheme 15 Pd-catalysed telomerization of butadiene with carbon dioxide with DACs as the solvent.⁷⁸

Among the DACs tested, reactions conducted in PC and EC showed higher selectivity (from 65% to ∼90%, respectively) towards lactone formation compared to linear carbonates and CH₃CN (ca. 40% selectivity in the latter case). The reactions carried out in GCP and GCB showed lower yields of δ-lactone compared to EC, PC and BC, leading to the hypothesis that the selectivity of the lactone may depend on the size of the additional substituent in the carbonate solvent.⁷⁸

DMC was proven to be the optimal green solvent for the chemo- and regio-selective Pd-catalysed allylation of biologically relevant heteroarenes (Scheme 16).¹²⁴ The reaction displayed enhanced yields of the allylated compound compared to that employing DMF, 1,4-dioxane and CH₃CN (92%, 82%, 84% and 80% isolated yield, respectively).¹²⁴

Scheme 16 Pd-catalysed allylation of biologically relevant heteroarenes with allyl alcohols.¹²⁴

In addition, DMC was found to be a suitable replacement for toluene and CH₂Cl₂ in the selective cyclocarbonylation of allyl phenol derivatives for the synthesis of lactones (Scheme 17).¹²⁵ However it must be mentioned that in some cases, DMC behaved as a ring-opening reagent, producing methoxycarbonyl compounds when the reactions were conducted for longer periods (48 h) and at higher temperatures (120 °C).¹²⁵

Scheme 17 Cyclocarbonylation of allyl phenol derivatives for the synthesis of lactones with DMC as the solvent.¹²⁵

Partial Pd/C hydrogenation of a fatty acid methyl ester (FAME) mixture was performed in DMC as the medium by Quaranta and co-workers. However, in this case study, lower conversion (37%) and selectivity values were obtained compared to when n-heptane was employed under mild conditions (conversion and selectivity of 97.8% and 81.1%, respectively).¹²⁶

Gautam et al. demonstrated that PC and EC can be used as green solvents for the Pd/C-catalysed phenoxycarbonylation of aryl iodides in the presence of N-formylsaccharin as a CO surrogate, yielding a library of different phenyl esters (Scheme 18).¹²⁷ PC displayed higher substrate conversion compared to EC (76% and 67%, respectively), while complete selectivity towards the desired product was achieved in both cases.¹²⁷

Scheme 18 Pd/C-catalysed phenoxycarbonylation of aryl iodides using DACs as the solvent.¹²⁷

Coupling reactions. Ismael et al. investigated the optimum solvent system for several Pd-catalysed carbonylative couplings namely, carbonylative cross-couplings (Scheme 19A), aminocarbonylations (Scheme 19B), and alkoxycarbonylations (Scheme 19C). Besides the carbonylative cross-coupling between m-tolylboronic acid and 3-bromoanisole, in which the use of DMC led to a final yield of only 16% (Scheme 19A), all the other reactions could be successfully carried out using DACs as the solvent such as DMC, DEC, EC and PC.¹²⁸ Specifically, the Pd-catalysed aminocarbonylation reaction of aryl bromides led to excellent yields employing DMC and DEC as solvents (97% and 94% yield, respectively); good results were also achieved in the presence of PC (80% yield; Scheme 19B).¹²⁸

Scheme 19 Pd-catalysed (A) carbonylative couplings of m-tolylboronic acid and 3-bromoanisole; (B) aminocarbonylation reaction of aryl bromides; and (C) alkoxycarbonylation reactions using DACs as the media. ^a Reactions conducted in DMC led to the formation of the methoxycarbonylated analogue isolated in 93% yield.¹²⁸

Pd-catalysed alkoxycarbonylation reactions gave the best results when performed in 2-Me-THF (91% yield), while DEC, EC and PC only led to moderate yields (45%, 30%, and 60%, respectively; Scheme 19C). Alternatively, the reaction conducted in the presence of DMC gave the methoxycarbonylated analogue in 93% isolated yield,¹²⁸ highlighting the capabilities of OCs as both reactants and reagents.⁵¹

Suzuki–Miyaura and Sonogashira coupling. Among the green solvents, DEC and DMC were shown to be viable alternatives to THF in the Pd-catalysed Suzuki–Miyaura coupling of selected amides (Scheme 20A).¹²⁹ The cyclic carbonate PC was also tested, without displaying encouraging results (37% yield). From a kinetic point of view, DACs showed lower reactivity compared to other solvent tested such as i-PrOAc, cyclopentyl methyl ether (CPME) and methyl tert-butyl ether (MTBE).¹²⁹ Unfortunately, DEC displayed inconsistent yields when both the starting amide and boronic acid were substituted with more hindered or electronically deactivated functional groups (yield values ranging from <5% to 89%).¹²⁹

Scheme 20 (A) Suzuki–Miyaura cross coupling of amides with DACs as the media;¹²⁹ (B) Suzuki–Miyaura coupling with different heterocyclic compounds using PC as the solvent;¹³⁰ (C) carbonylative Suzuki–Miyaura and Sonogashira cross-coupling reactions in PC;¹³⁴ and (D) Sonogashira cross-coupling reaction of aryl chlorides in PC.¹³³

Several researchers employed PC as the solvent in the Suzuki–Miyaura and Sonogashira coupling reactions. Czompa et al. reported that different heterocyclic compounds, i.e., 2-iodopyridine, 4-iodopyridine and 6-iodopyridazin-3(2H)-one and various boronic acids can be used as starting materials (Scheme 20B) both under microwave conditions and conventional oil bath heating.¹³⁰ All the reactions proceeded with good to excellent yields (from 43% to 92% under conventional heating and from 50% to 93% under microwave irradiation) of the corresponding coupling products. However, in the case of pyridazinones, 2-hydroxypropyl-chain-containing side-products were observed due to the ring opening of the cyclic OC.¹³⁰

In another example, PC was used as the medium in carbonylative Suzuki–Miyaura and Sonogashira cross-coupling reactions catalysed by the aminophosphine pincer complex {[C₆H₃-2,6-(NHP{piperidinyl}₂)₂]Pd(Cl)}(III) (Scheme 20C).¹³⁴ In fact, carbonylation reactions are known to proceed efficiently in cyclic OCs, and thus can be effectively employed for the substitution of other toxic solvents, i.e., anisole, toluene, dioxane, DMA, MTBE, and DMF.¹³⁴ The reactions proceeded with yields in the range of 70%–80% for both Sonogashira and Suzuki–Miyaura carbonylative cross-coupling.¹³⁴

Finally, Torborg et al. employed PC as the solvent for the Pd-catalysed Sonogashira cross-coupling reaction of aryl chlorides in the presence of N-substituted heteroaryl phosphines without copper co-catalysts (Scheme 20D).¹³³ The reaction of 3-chlorothiophene and 1-octyne was tested using PC as the solvent at 90 °C, leading to 76% yield of the cross-coupling product. It should be mentioned that PC can also partially displace the ligand, and thus the reaction required a higher Pd/ligand ratio. In contrast, the Sonogashira coupling in toluene with sodium carbonate as the base yielded the desired 3-octinylthiophene in good yield at a lower ligand concentration.¹³³

Heck coupling. EC was found to be an excellent reaction medium for Heck coupling, with complete substrate conversion and yields of up to 99% under microwave (MW) irradiation (Scheme 21). The Pd-based catalyst was supported on a humin-like resin obtained from 2,5-bis(hydroxymethyl)furan (DHMF) and maleic anhydride and successively encapsulated by in situ polymerization.¹³²

Scheme 21 Pd-catalysed Heck coupling reaction in EC as the solvent.¹³²

The same reaction was also tested in DMC, DEC and GC without obtaining comparable results (30%, 30% and 10% yield, respectively).

The highest performance for EC was ascribed to its degradation and release of CO₂ upon heating, whose dissolution in the reaction media facilitated Pd solubilization, as previously reported in the literature.^168,169 This resulted in an increase in the reaction rate because the Heck reaction occurs homogeneously in the organic phase. However, due to the thermal degradation of EC, its recovery and reuse could not be performed.¹³²

Other studies also reported the ability of PC to act as a colloidal palladium stabilizer. Subsequently, the colloidal solution can catalyse Heck reactions in the absence of phosphine ligands. Given that catalysis is likely to occur on the surface of the clusters, these processes are probably more related to heterogeneous than to homogeneous catalysis.¹⁷⁰

4.9 Ni-catalysed reactions

DMC was successfully employed as a green medium substitute for toluene in the hydrodeacetoxylation of aryl acetates mediated by pinacolborane (HBpin) and a nickel-N-heterocyclic carbene (NHC) catalytic system, yielding the corresponding deoxygenated arenes (yields between 46% and 90%).¹³⁶

4.10 Pt-catalysed reactions

PC was applied as a co-solvent in the platinum-catalysed hydrosilylation of unsaturated fatty acids.^137,138 In particular, the introduction of a ternary solvent system formed by cyclohexane/toluene/PC allowed the recycle and reuse of the catalyst even if hydrogenation and double bond isomerization of the starting reagent were reported to occur as side reactions.¹³⁷

Moreover, a mixture of cyclohexane/PC and n-hexane/PC could be employed for the recycling of the catalyst in these reactions.^137,138

4.11 Ru-catalysed olefin metathesis

Olefin metathesis is almost exclusively carried out in dichloromethane and aromatic solvents (benzene, toluene, and chlorobenzene). However, efficient metathesis transformations can be performed in DMC and PC, given that they were shown to be compatible with ruthenium-catalysed olefin metathesis reactions.^139–141

Miao et al. reported a series of olefin metathesis transformations, i.e., ring-closing metathesis (RCM), cross-metathesis and ethenolysis of methyl oleate, which could be performed in dimethyl carbonate and CH₂Cl₂ (or aromatic solvents) with comparable results (Scheme 22). In some cases, the RCM reactions proceeded faster in DMC than in CH₂Cl₂, despite displaying similar yields.¹³⁹

Scheme 22 Olefin (A) ring-closing metathesis; (B) cross-metathesis and (C) ethenolysis in DMC.¹³⁹

Huang et al. reported the use of PC as a suitable solvent for the ruthenium RCM and cross-metathesis transformations of a variety of substrates including renewable fatty esters (Scheme 23).¹⁴⁰

Scheme 23 Olefin (A) ring-closing metathesis and (B) cross-metathesis in PC.¹⁴⁰

Ru-catalysed enyne cross-metathesis of several alkyne derivatives with terminal olefins could also be performed under mild conditions in DMC, substituting dichloromethane and toluene.

A one-pot reaction based on an ethenolysis step followed by an enyne cross-metathesis allowed the efficient transformation of renewable unsaturated fatty esters into valuable conjugated 1,3-dienes.¹⁴¹ This new reaction sequence provides a useful method in oleochemistry for the conversion of natural oils into functional compounds or intermediates of interest for further transformations.¹⁴¹

DMC was also employed as the solvent, substituting toluene, in both ethenolysis and cross-metathesis reactions using different renewable fatty esters, i.e., methyl oleate (Scheme 24A), dimethyl octadec-9-enedioate (Scheme 24B) and methyl ricinoleate (Scheme 24C), yielding conjugated 1,3-dienes of interest for further transformations. This protocol allowed the ene–yne cross-metathesis reaction to be carried out with long-chain terminal olefins and in one-pot with internal olefins after shortening by ethenolysis.¹⁴²

Scheme 24 Two-step ethenolysis/ene–yne cross-metathesis starting from (A) methyl oleate, (B) dimethyl octadec-9-enedioate and (C) methyl ricinoleate in DMC as the solvent. Yields calculated using GC.¹⁴²

In addition, cross-metathesis reactions of dec-1-ene and methyl undec-10-enoate with various terminal and internal propargylic acetates and carbonates were tested in toluene and DMC (yield values between 70%–95% in the former case and 54%–74% in the latter).¹⁴²

4.12 Organic carbonates and ionic liquids as media in organic synthesis

The combination of ionic liquids and OCs as solvent systems was shown to perform a wide variety of different organic transformations. Particularly, cyclic DACs showed appreciable results for the synthesis of organic compounds in combination with ionic liquids. In fact, PC and supercritical CO₂ (scCO₂) were applied as solvents for the continuous synthesis of D,L-α-tocopherol using a sulfonic acid-functionalized ionic liquid as the catalyst (yields up to 90%). D,L-α-Tocopherol is the main composition of vitamin E and plays an important role in human health due to its antioxidative capacity and ability to act as a free radical scavenger.¹⁴⁴

Moreover, the cycloisomerization of N-(prop-2-yn-yl)benzamide to 2-phenyl-5-vinylidene-2-oxazoline in the presence of NHC–Au–X [NHC = (1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene), X⁻ = BF₄⁻, OTf⁻, OTs⁻, and TFA⁻] as catalysts was carried out in PC, among others, as the medium (Scheme 25).¹⁴⁵ However, it must be mentioned that in this case, the green solvents showed, on average, slower conversion with respect to volatile organic solvents (VOS) (conversion_PC: 49%, TOF_PC: 180 h⁻¹ vs. conversion_CH2Cl2: 89%, and TOF_CH2Cl2: 406 h⁻¹).¹⁴⁵

Scheme 25 Cycloisomerization of N-(prop-2-yn-yl)benzamide to 2-phenyl-5-vinylidene-2-oxazoline in the presence of NHC–Au–X in PC.¹⁴⁵

The vitamin B1 like-derived acidic ionic liquid [HMTH]₂H₂[SiW₁₂O₄₀] coupled with DMC, PC and EC as solvents was found to be an efficient heterogeneous catalyst for the direct dehydrative coupling of alcohols with alcohols or alkenes to synthesize various polysubstituted olefins. Excellent yields of the desired compounds were obtained (93% yield at 120 °C for 15 min, 3% catalyst loading) with DMC as a green solvent, while the reaction proceeded with good yields in PC and EC (66% and 37%, respectively).¹³¹

4.13 Phase transfer catalysis

DMC was tested together with methyl-tert-amyl ether (MTAE), 5-methyl-2-hexanone (MIAK) and MIBK as alternative media to toluene and chlorobenzene for phase-transfer catalysed (PTC) reactions in organic media. The experiments were conducted by dissolving different quaternary ammonium salts (Q⁺Y⁻), i.e., MeBu₃N⁺Cl⁻, MeBu₃N⁺, p-NO₂C₆H₄O⁻, Bu₄N⁺Cl⁻, Bu₄N⁺Br⁻, Bu₄N⁺p-NO₂C₆H₄O⁻, Hexyl₄N⁺Cl⁻, Hexyl₄N⁺Br⁻, Hexyl₄N⁺p-NO₂C₆H₄O⁻, Octyl₃MeN⁺Cl⁻, Octyl₄N⁺Br⁻, and Bu₃P⁺C₁₆H₃₃Br⁻ in the selected organic media and a water solution containing the corresponding sodium salt (Na⁺Y⁻). The data showed that in these media, the partition of the catalyst in the organic phase is comparable to or higher than that in chlorobenzene.¹⁴⁶ In particular, the solubility in DMC was similar with that in chlorobenzene under both homogeneous and heterogeneous conditions, and hence DMC represents a valid greener alternative to the solvents traditionally used in PTC processes.¹⁴⁶

4.14 Enantioselective reactions

EC and PC have been shown to be excellent media for several asymmetric reactions, i.e., aldol reactions,^150,171,172 hydrogenation of non-functionalized olefins,^147,148 cyanohydrin trimethylsilyl ether synthesis,¹⁴⁹ and α-hydrazination of aldehydes and ketones,¹⁵¹ substituting the most employed toxic solvents such as DMF, DMSO, CH₂Cl₂ and CH₃CN (Scheme 26). In all cases, chemical yields of up to 99%, diastereoselectivity of up to 100% and enantioselectivity up to 99% were obtained.¹⁵⁰

Scheme 26 Asymmetric reactions using EC and PC as green solvents: (A) asymmetric aldol reaction; (B) α-hydrazination of aldehydes and ketones; (C) synthesis of cyanohydrin trimethylsilyl ethers; and (D) asymmetric hydrogenation of non-functionalized olefins.

4.15 Photocatalytic reactions

Photocatalytic reactions were reported in the literature using DMC as the medium under both UV and visible light irradiation (Table 4 and Scheme 27).

Scheme 27 Examples of 3-alkylation of 2-aryl-2H-indazoles in DMC.¹⁵²

Table 4 Photocatalytic reactions performed with organic carbonates as the media

#	Reaction type	Organic carbonate	Reagent(s)	Product(s)	Catalysts	Yield (%)	Ref.
a Conversion values.b Selectivity values.
1	Decarboxylative 3-alkylation	DMC			4CzIPN, blue led	41–91	152
2	CH bond arylation	DMC			Ru(bpy)3Cl2, Pd(OAc)2, visible light	67–94	153
3	Oxidative hydroxylation	DMC		R–OH	7H-Benzo[c]thioxanthen-7-one, visible light	81–97	157
4	Alcohol oxidation	DMC	R–OH		TiO2(C/T), visible light	64–95^a, 92–99^b	156
5	1,3-Diene derived quinolinone compounds	DMC			4CzIPN, blue led	13–93	158
6	Aroylated heterocycles	DMC			Catalyst free, visible light, blue led	40–95	155

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A transition-metal-free photocatalytic decarboxylative 3-alkylation reaction of 2-aryl-2H-indazoles was developed under visible-light irradiation (#1, Table 4 and Scheme 27). By employing 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as the photocatalyst, and alkyl N-hydroxyphthalimide esters as the alkylating reagents, various primary, secondary, and tertiary alkylated 2-aryl-2H-indazoles were synthesized in moderate to good yields (41%–91%). 2-Aryl-2H-indazoles containing strong electron-withdrawing substituents (4-NO₂ and 4-CN) showed no reactivity in these conditions. Moreover, the protocol was successfully applied to the late-stage modification of drug molecules such as Pazopanib, ER-16b, Niraparib, and WAY-214950.¹⁵²

Furthermore, DMC was shown to be a suitable solvent for (i) the direct CH bond arylation of anilides later applied for the gram-scale synthesis of the fungicide Boscalid (81% isolated yield; #2, Table 4);¹⁵³ (ii) the aerobic oxidative hydroxylation of boronic acids (#3, Table 4);¹⁵⁷ (iii) the oxidation of diverse alcohols (#4, Table 4)¹⁵⁶ and (iv) the synthesis of 1,3-diene-derived quinolinone compounds (#5, Table 4).¹⁵⁸

Additionally, Zeng and co-workers developed a visible-light-induced strategy for the construction of various aroylated heterocycles, including the modification of pharmaceuticals and natural products, i.e., thioflavones, benzimidazo[2,1-a]isoquinolin-6(5H)-ones, indolo[2,1-a]isoquinolin-6(5H)ones, quaternary 3,3-dialkyl 2-oxindoles, inoxaline-2(1H)-ones, and benzo[e][1,2,3] oxathiazine 2,2-dioxides in DMC (#6, Table 4).¹⁵⁵

4.16 Other reactions/applications of organic carbonates as media in organic synthesis

Condensation/rehydration reaction. The perfume additive Florol® is widely used in the fragrance industry, which could be synthesized via a condensation and rehydration reaction starting from isoprenol and isovaleraldehyde using DMC as the solvent. The reaction was performed in the presence of microporous H-Beta-300 with an SiO₂/Al₂O₃ ratio of 300 (72% selectivity and 99% conversion) at 40 °C.¹⁵⁹

Radziszewski reaction. PC was employed as alternative medium for the preparation of 2,4,5-triaryl imidazoles in the Radziszewski reaction as a substitute for DMSO and DMF (Scheme 28). A wide range of 2,4,5-triaryl-substituted imidazoles was synthesized. PC offered advantages not only in the yield of the reaction but also in the isolation of the product, which involved simple filtration, followed by washing with warm water.¹⁶⁰

Scheme 28 Synthesis of 2,4,5-triaryl imidazoles via the Radziszewski reaction with PC as the medium.¹⁶⁰

Cyclodextrin-based supramolecular assemblies. DEC and methanol were used as media to fabricate 2-O-methylated β-cyclodextrin (2-Me-β-CD)-based supramolecular assemblies with diverse morphologies on a polyethylene terephthalate (PET) substrate.¹⁶¹

Complexation reactions. PC and its mixtures with other solvents, i.e., DMF, H₂O and MeOH, were studied as media for the complexation reaction between the UO₂²⁺ cation with diaza-15-crown-5 (DA15C5) using the conductometric method. The stability of the (DA15C5.UO₂²⁺) complex in the pure studied solvents was found to follow the order of PC > H₂O > DMF ≫ MeOH.¹⁶²

Claisen rearrangement. Thermal aromatic Claisen rearrangement of allyl–aryl ethers to obtain ortho-allyl phenols (naphthols) was performed employing PC as the solvent. The reactions performed in PC resulted in an increase in the product yield (70–83%) and significantly shortened the reaction time (1–6 h) compared with 1,2-dichlorobenzene (DCB; 52–75%; 10–40 h) traditionally employed in this type of Claisen rearrangement.¹⁶³

Ring-opening reactions. Righi et al. showed that several ring-opening methodologies catalysed by MgBr₂, LiBr/Amb15, NaBr/Amberlyst-15 and BF₃·Et₂O/TMSN₃ could be performed in DMC instead of the usually employed solvents, i.e., dichloromethane, Et₂O and CH₃CN. In the newly developed procedures, the stereo- and regio-selectivity were conserved and the work-up was simplified, only requiring filtration, and therefore considerably reducing the amount of solvent employed in the processes.¹⁶⁴ The substrates employed with these methodologies included epoxy alcohols, silylated aziridino alcohols, epoxy- and aziridino-esters, vinyl epoxides and vinyl aziridines.¹⁶⁴

All the reactions were performed at room temperature, and the only noticeable difference was in the reaction times (10 h DMC vs. 2–4 h Et₂O; 1–2 h DMC vs. 5 h CH₃CN), while the isolated product yields varied from 70% to 99%.¹⁶⁴

5. Organic carbonates in polymerization and depolymerization reactions

OCs such as PC, EC, DMC have been efficiently employed for different types of polymerizations,^173–177 including electroploymerization,^178–187 photopolymerization,^188,189 as well as depolymerization reactions. Regarding the latter topic, studies have been reported on the depolymerization of cellulosic paper towels,¹⁹⁰ solvolysis of cellulose,¹⁹¹ liquefaction of newspaper¹⁹² and lignin depolymerization.¹⁹³

5.1 Radical polymerizations

An example of radical polymerization conducted in OCs is the copolymerization of polyethylenes with a low ketone content, which was carried out using DMC or under aqueous conditions at pressures <350 atm.¹⁷⁶

DAC/water biphasic systems composed of DEC, DMC, PC and EC were also shown to be suitable for single electron transfer Living radical polymerization (SET-LRP) as substitutes for THF and 1,4-dioxane.¹⁷⁵ The SET process involves the transfer of a single electron from an electron donor (i.e., Cu(0) and Cu(I)X catalysts) to an electron acceptor, which can be situated in two different molecules or in two sites of a single compound.¹⁹⁴ This mechanism can be exploited for the promotion of different chemical transformations in biology, electrochemistry and polymer chemistry.¹⁹⁴ DEC as well as other nonpolar solvents i.e., ethyl acetate, toluene, anisole, and cyclohexane, were shown to mediate the SET-LRP of n-butyl acrylate (BA) in ethanol/water mixtures at a 4.0 : 4.0 : 2.0 volume ratio instead of hexane.¹⁷⁴

Similarly, EC was investigated as the solvent in atom transfer radical polymerization (ATRP).¹⁷³ In ATRP, the radical species are generated through a reversible red-ox process catalysed by a transition metal complex (M_tⁿ–Y/Ligand, Scheme 29, top side). This process is regulated by the activation (k_act) and deactivation (k_deact) constants. Similar to radical polymerization mechanisms, polymer chains propagate by the addition of the intermediate radicals to monomers (propagation constant, k_p). Moreover, in ATRP, termination reactions (termination constant, k_t) rarely occur majorly through radical coupling and disproportionation.¹⁹⁵

Scheme 29 General mechanism for ATRP (top) and ATRP of MEA in EC as the medium.^173,195

For example, the ATRP of 2-methoxy ethyl acrylate (MEA) was carried out in the presence of methyl 2-bromopropionate (MBP) as the initiator and CuBr/N,N,N0,N0,N00-pentamethyldiethylenetriamine (PMDETA) as the catalyst system (Scheme 29, bottom side).¹⁷³ The resulting polymers were compared to that obtained using toluene as the medium, showing similar results in terms of M_n and M_w/M_n. In addition, both polymers displayed a narrow molecular weight distribution.¹⁷³

5.2 Electropolymerization

Electropolymerization techniques allow the production of polymeric or inorganic films with precise spatial resolution using the standard three-electrode configuration (working electrode, reference electrode, and counter electrode) in an electrochemical cell dipped in an electrolytic solution (Scheme 30). After the potential is applied, a polymeric thin film starts growing on the surface of the working electrode.^196,197

Scheme 30 Electropolymerization using DACs as the media. (A) Pyrrole electropolymerization;¹⁹⁹ (B) thiophene electropolymerization;²⁰⁰ and (C) N-methylaniline (NMA) and N-butylaniline (NBA) electropolymerizations; mechanism modified from.¹⁸³ ITO: indium tin oxide, TO: tin oxide.

The obtained polymers can be applied in batteries, conductive textiles and fabrics, antistatic coatings, supercapacitors and special sensors.¹⁷⁸ It should be mentioned that the solvent affects the electrochemical activity, conductivity, and morphology of the resulting polymer.¹⁹⁸ Therefore, the solvent choice is particularly important given that it provides an ionic conducting medium. It must possess a high relative permittivity, and it must be stable at the oxidation potential of the monomer. PC was reported to be an ideal solvent given that it fulfils all these characteristics.¹⁷⁸

Pyrrole electropolymerization. Electropolymerization in PC is mainly utilized for monomers such as pyrrole, thiophene, and aniline derivatives, but some applications can also be found for styrene¹⁸⁴ and acetylenes.^185,186 Several works reported pyrrole electropolymerization on zinc¹⁷⁹ and zinc–lead–silver alloy¹⁸⁰ electrodes in PC. The use of this medium in the presence of p-toluene sulfonate counterions showed improved results compared to other solvents, i.e., CH₃CN and nitrobenzene, obtaining high-quality, homogeneous and thick coatings (Scheme 30A).¹⁸⁰

Polythiophene and 2,2′-bithienyl electropolymerization. Many derivatives of thiophene¹⁸¹ and bithiophenes¹⁸² were used as substrates for electropolymerization in PC. For example, Tachibana and co-workers achieved a conductive fine line patterns after the electropolymerization of dissolved UV-exposed polysilanes (Scheme 30B).¹⁸¹ Notably, PC was suitable for the electropolymerization of 2,2-bithiophene, revealing that although the reaction was thermodynamically and kinetically favoured in CH₃CN, better morphologies and enhanced mechanical stabilities could be obtained in PC.¹⁸²

Moreover, electropolymerization of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and tetrafluoroborate was carried out in PC as the medium to create coatings for metal electrodes, which possessed similar proprieties to that obtained in CH₃CN. The coatings prepared with PC displayed excellent electrochemical stability and survived autoclave sterilization, prolonged soaking, and electrical stimulation without major changes in their electrochemical properties.¹⁸⁷

Aniline and methyl aniline electropolymerization. Mixtures of PC and water (80% water; 10%–20% PC) were shown to enhance the electropolymerization of N-methylaniline (NMA) and N-butylaniline (NBA), yielding narrower molar weight distributions and higher electrical conductivities compared to when DMF and DMSO mixtures were employed (Scheme 30C).¹⁸³

5.3 Photopolymerization

DMC/CH₃CN solvent system favoured the photoinduced polyaddition reaction between α,ω-diiodoperfluoroalkanes and α,ω-unconjugated dienes instead of chain transfer reactions, generating a high yield (76.5%) and high molecular weight (M_n,GPC = 9400 g mol⁻¹) perfluorocarbon-containing alternating copolymers. The polymerization was performed under irradiation with blue light emitting diodes (LEDs) at room temperature (25 °C, Scheme 31).¹⁸⁸

Scheme 31 Photoinduced step transfer-addition and radical-termination (START) polymerization between α,ω-diiodoperfluoroalkanes and α,ω-unconjugated dienes in a mixture of DMC and CH₃CN as the media.¹⁸⁸

Kim et al. reported DMC as the most efficient solvent among more than 40 solvents for the free radical photopolymerization of alkenes, including vinylidene fluoride (VDF), vinyl acetate, methyl methacrylate, styrene, and butadiene.¹⁸⁹

5.4 Depolymerization

The degradation and decomposition of cellulose were studied in the acid-catalysed solvolysis treatment of biomass using polyethylene glycol (PEG) and EC. EC was shown to promote the faster degradation of cellulose compared to PEG, leading to the formation of glucosides, which then decomposed, resulting in a levulinic acid structure (Scheme 32).¹⁹¹ DMC was instead employed as a trapping agent for EG in the depolymerization of polyester fibres from textile products.²⁰¹

Scheme 32 Acid-catalysed solvolysis for the decomposition of cellulose in an EC-PEG system.¹⁹¹

Furthermore, PC, EC, DMC and their mixtures with water were investigated as green co-solvents for the MW-assisted depolymerization of cellulosic paper towel waste catalysed by dilute sulfuric acid, replacing DMSO and THF. PC/H₂O and EC/H₂O enhanced the depolymerization of paper towel waste and improved the total sugar yield (up to ca. 25 C mol%) compared to H₂O only (up to ca. 11 C mol%) under mild reaction conditions (130 °C, 20 min). The higher performance of PC/H₂O and EC/H₂O can be attributed to the higher availability of reactive protons in the catalytic system, which facilitates efficient acid hydrolysis of the recalcitrant cellulosic fibres.¹⁹⁰ However, the high boiling point (242–248 °C) of these solvents can be challenging for product separation and solvent recovery by distillation.¹⁹⁰

5.5 Resin preparation

DMC proved to be useful as a solvent in the synthesis of a bio-based phthalonitrile (PN) resin via the nucleophilic substitution reaction between 4-nitrophthalonitrile and Schiff base bisphenol (VTBP, obtained by reacting vanillin and tyramine in ethanol) (Scheme 33). To further increase the sustainability of the procedure, DMC was recovered and reused.²⁰²

Scheme 33 Synthesis of a bio-based phthalonitrile (PN) resin (VTPN) via the nucleophilic substitution reaction between 4-nitrophthalonitrile and Schiff base bisphenol (VTBP). VTPB was obtained by reacting vanillin and tyramine in ethanol.²⁰²

5.6 RAFT/MADIX co-polymerization

DMC was used as the medium for the co-polymerization reactions between tetrafluoroethylene (TFE) and isobutyl vinyl ether (iBuVE) via both conventional radical and reversible addition–fragmentation chain transfer polymerization/macromolecular design via the interchange of xanthates (RAFT/MADIX) method.²⁰³ The RAFT/MADIX method enables control of the chain growth in radical polymerization through the dynamic equilibrium between the growing chains and dormant chains based on reversible transfer or termination reactions (Scheme 34). This technology can be used to design complex functional architectures in the bulk, organic solvents and water.²⁰⁴

Scheme 34 RAFT/MADIX general mechanism (framed reactions); co-polymerization between tetrafluoroethylene (TFE) and isobutyl vinyl ether (iBuVE) via RAFT/MADIX in DMC as the medium.^203,204

In particular, O-ethyl-S-(1-methyloxycarbonyl)ethyl xanthate and benzoyl peroxide (BPO) were used as the RAFT chain transfer agent and initiator, respectively, yielding alternating copolymers (poly(TFE-alt-iBuVE)) (Scheme 34). The molar masses varied between 11 000 and 4400 g mol⁻¹ with a broad dispersity (Đ = 2) with the conventional method and from 1200 to 2000 g mol⁻¹ and narrower Đ (1.08–1.11) via RAFT/MADIX.²⁰³

Furthermore, Guerre et al.²⁰⁵ demonstrated that radical DMC fragments were generated during the polymerization of vinylidene fluoride (VDF) through a proton transfer process. This may initiate further polymerization or termination of other macroradicals by recombination.²⁰³ Proton transfer from DMC or the vinyl ether monomer to the macroradical was observed in uncontrolled copolymerization, whereas much less proton transfer from DMC was noted in RAFT copolymerization.²⁰³

5.7 Polymer crystallization

In a reported study, poly(2-isopropyl-2-oxazoline) (PIPOx) crystallization was performed in either DMSO or PC, generating polymers with a higher crystalline content than PIPOx crystallized in CH₃CN.²⁰⁶

In addition, porous structures were prepared by extrusion-based 3D printing of biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) using EC as a crystallizable and water-extractable solvent.²⁰⁷

5.8 Post-polymerization modifications

Woodfield and co-workers presented a post-polymerization modification to prepare sulfobetaine co-polymers by employing an activated ester precursor, poly-(pentafluorophenyl acrylate), a zwitterionic amine, 3-((3-aminopropyl)dimethylammonio) propane-1-sulfonate, and ADPS (and ADPS mixtures with other amines) with PC as the solvent (Scheme 35).²⁰⁸ The scope of activated esters was also investigated, thus providing synthetic access to a library of well-defined hydrophobically modified zwitterionic co-polymers.²⁰⁸

Scheme 35 Sulfobetaine co-polymers via poly(pentafluorophenyl acrylate), pPFPA as activated ester in combination with ADPS and other amines in PC as the solvent.²⁰⁸

5.9 Lignin-derived polymers

DMC was employed as the solvent instead of dichloromethane for the curing of lignin and plant oils via olefin metathesis to produce thermosetting polymer films. The resulting materials displayed similar Young's moduli and tensile strength, but that produced with DMC showed a lower degree of cross-linking compared to the films produced in CH₂Cl₂.¹⁹³ Diallyl carbonate (DAllC) was also used as media to suspend organosolv lignin (OL) and prepare allylated lignin.¹⁹³

5.10 Preparation of polyurethane (PU) adhesives

Polyols, which are important compounds of polyurethane adhesives (PU), were prepared by liquefying beech wood sawdust²⁰⁹ and hardwood residue (HR)²¹⁰ with EC and sulfuric acid. The obtained bio-polyol was used for the preparation of two types of PU adhesive by blending two types of isocyanates, poly4,4′-diphenyl methane diisocyanate (PMDI) and toluene diisocyanate (TDI), in different NCO/OH ratios.²⁰⁹ EC can restrain the free radical produced by the lignin fragments, and then stop the recondensation in the liquefaction process.²¹⁰ On this topic, Yamada and Liang^211,212 reported that the rate of liquefaction of cellulose and hardwood in EC and PC is almost 30-times faster than other solvents such as polyhydric alcohols, which is probably due to the high permittivity of cyclic carbonates.²⁰⁹

5.11 Microencapsulation

DMC and PC were used as solvents to fabricate poly(D,L-lactide-co-glycolide) (PLGA) microspheres²¹³ and nanoparticles, respectively.²¹⁴ In the former case, DMC was employed as a green dispersion solvent, creating an oil-in-water emulsion made by PLGA/Nile red/progesterone/DMC in the aqueous phase. The subsequent addition of an NaOH solution to the emulsion led to the decomposition of DMC, which partitioned to the water phase, thus allowing the continuous diffusion of DMC existing in emulsion droplets into the aqueous phase and its complete removal. This process allowed the uniform distribution of Nile red across the microsphere matrix. In addition, the drug crystallization phenomenon commonly observed in conventional emulsion-templated processes was inhibited by increasing the hydrolysis rate of DMC. The green solvent hydrolysis-based microencapsulation technique can be a promising alternative to conventional microencapsulation methods using toxic halogenated organic solvents.²¹³

In addition, small transparent PLGA nanoparticles (below 70 nm) were obtained by an emulsification-diffusion method employing PC as the medium. Alternatively, larger PLGA nanoparticles (above 290 nm) were obtained using acetone and CH₂Cl₂.²¹⁴ The small particle sizes for PC were attributed to both the adequacy of the stabilizer protection against coalescence and the low interfacial tension between the aqueous and organic phases, resulting from their partially water-soluble nature.²¹⁴

6. Organic carbonates in CO₂ capture

The combination of DMC as a solvent and either polydimethylsiloxane (PDMS)/TiO₂ or (PDMTS)–SiO₂ nanocomposites can be used as a CO₂ capture method due to the high solubility of CO₂ in DMC and its low desorption.^215–217 In this process, CO₂ is initially absorbed in DMC, and then CO₂ is desorbed by a pervaporation (PV) membrane from the rich liquid solvent, allowing ca. 72% of energy savings compared to conventional CO₂ capture methods.²¹⁸ In addition, diethylenetriamine (DETA) dissolved in different solvents, including ethanol, diethylene glycol dimethyl ether, NMP or DMC, can be effectively used as a CO₂ absorber. Single crystals of DETA-carbamate indicated that one mole DETA can absorb one mole of CO₂ to form precipitates in organic solvents.²¹⁹

DEC was also shown to perform as a good CO₂ absorbent with even better results in terms of liquid–gas ratio, absorption temperature, desorption temperature and N₂ flow on CO₂ absorptivity compared to DMC.²²⁰

Therefore, DMC and DEC were tested as additives to dimethyl ethers of polyethylene glycol (DEPG) for the removal of acid gas such as CO₂ and H₂S in the Selexol™ process due to their strong CO₂ adsorbing characteristics.^221–223 The results showed that the addition of DMC and DEC led to reduced net utility costs compared to the normal Selexol™ process. However, a major drawback of DMC and DEC is the vast solvent loss during the solvent regeneration stage. This increases the solvent make-up cost by too much for them to be economically competitive.²²³ Alternatively, PC showed promising performances as a physical absorbent for biogas upgrading, with a 30% specific cost reduction compared to when water was employed.²²⁴

7. Organic carbonates as solvents for the preparation of membranes, films and fibres

The intrinsic proprieties of membrane-based processes make them simple, flexible, selective and an environmentally friendly technology, which require low energy consumption as well as simple scale-up and operational conditions.^225–227 Membrane processes are effectively employed in a wide variety of industrial applications including the separation of complex mixtures, hydrogen isolation,²²⁸ CO₂ removal,²²⁹ wastewater treatment²³⁰ and water desalination,^231,232 allowing up to 50% of energy savings in the production cost compared to other traditional separation technologies.²²⁹ Nevertheless, most of the commonly employed solvents in this field such as NMP, DMF and DMA display cancerogenic and teratogenic effects,²³³ present high volatility, and thus represent a threat to the ecosystem and human beings.^234,235

Replacing traditional toxic solvents with greener alternatives is not an easy task, given that they have a particular set of properties that play a crucial role in determining the final membrane morphology and performance.²³⁶ Solvent properties such as viscosity, dielectric constant, polarity and boiling point greatly affect the characteristics imparted to membranes during their formation.²³⁵

In this scenario, traditional solvents need to be replaced with greener solvents possibly synthesized in a sustainable way.

One of the possible solutions for these issues is the employment of OCs.^47,237 In fact, it has been reported that replacing NMP with EC in the preparation of PVDF membranes significantly reduced the overall environmental impact by up to 35% according to life cycle assessment analyses.²³⁶

Rasool and co-workers employed commercially available DMC, DEC, PC, 1,2-butylene carbonate, GC and the custom-made 1,2 hexylene carbonate and styrene carbonate (SC) as green solvents for membrane preparation using different polymers such as polyethersulphone (PES) and polyacrylonitrile (PAN) polyvinilydene fluoride (PVDF).²³⁷ Due to the solubility issues of most polymers in OCs, several mixtures were investigated to obtain suitable polymer–solvent compatibility for membrane casting (homogeneous polymeric solution). The investigated examples include OC/OC (i.e., SC/PC), OC/NMP and OC/methyl lactate.

7.1 Polyvinylidene fluoride membranes

Linear water-soluble OCs can be employed as green media for the preparation of polyvinylidene fluoride (PVDF) membranes both via non-solvent-induced phase separation (NIPS) and a combination of vapor-induced phase separation (VIPS)-NIPS techniques (Scheme 36). Phase inversion techniques involve the transformation of a polymeric solution into a solid polymeric matrix, which, in the case of NIPS, is achieved by the immersion of a cast polymeric solution in a non-solvent bath, while in VIPS, by the non-solvent vapor present in a climatic chamber.^225,238 Phase inversion methods are some of the most employed processes to prepare commercially available membranes. These methods are very versatile and allow the production of membranes with different morphologies.²³⁸

Scheme 36 Synthesis of non-commercial (methoxy ethyl) carbonates as solvents for the preparation of PVDF membranes.⁴⁷

The membranes obtained with custom-made DACs displayed greater structural resistance and a smaller pore size compared to that achieved using commercially available cyclic DACs. The collected data showed that it was possible to achieve a wide variety of dense and porous membranes by using a single family of compounds.⁴⁷

PC and diphenyl carbonate (DPC) were instead employed as diluents to prepare PVDF hollow fibre membranes through a triple-orifice spinneret in thermally induced phase separation (TIPS). In the TIPS technique, polymer precipitation is caused by a decrease in temperature, which can occur steadily or abruptly by immersion in a coagulation bath.²²⁵ Different concentrations of DPC and PC generated different membrane structures, showing significant effects on the permeability, rejection, and mechanical strength of the membrane.²³⁹ In particular, PC endowed all the membranes with a porous inner and outer surface (ca. 45% porosity and 5.5 μm average pore size), while dense structures were detected in the absence of PC.²⁴⁰ The mechanical strength of the PVDF membrane remained unchanged because of the negligible impact of the solvents used as the bore liquids on the membrane bulk structure.²⁴⁰ Similarly, PC was used as a co-extrusion solvent in the outer layer of a PVDF doping solution in the TIPS process, leading to significant improvements in the pure water permeability stability of the membrane.²⁴¹ The penetration of PC inside the membrane considerably changed its surface and sublayer structure.

In addition, the effects of the solvent and temperature on the crystal formation were investigated for vinylidene fluoride/trifluoroethylene copolymer (P(VDF-TrFE)). Highly crystalline vinylidene fluoride/trifluoroethylene copolymer P(VDF-TrFE) thin films were fabricated by spin casting using DEC as a polar solvent.²⁴²

7.2 Polylactic acid membranes

DMC can be also employed for the preparation of different types of polylactic acid (PLA) membranes as follows:

• PLA fibres via solution blow spinning (SBS), a technique allowing the production of micro- and nano-scale fibres from polymeric solutions through pressurized air using a specialized nozzle;²⁴³

• PLA porous bioactive nanofibers through SBS combined with thermally induced phase separation;²⁴⁴

• Electrospun nanofibrous supports made of PLA and gelatin.²⁴⁵ Then, the support was used for the production of green thin-film composite (TFC) membranes, which can offer a sustainable solution for the separation of complex mixtures in aqueous and organic solvent nanofiltration (OSN).²⁴⁵ The electrospinning of PLA from DMC solutions produced ultrafine nanofibers in the presence of ammonium salt as an additive.²⁴⁵

PLA was also used in combination with bamboo fibres in the presence of DMC to produce a bio-based membrane applicable as a membrane backing material. The bio-based membrane supports exhibited a porous structure (porosity of 0.719 ± 0.132) with tensile strength (32.7–73.3 MPa) comparable to conventional materials, such as polypropylene. The synthesized supports were found to be stable in green polar aprotic solvents including Cyrene, 2-Me-THF, γ-valerolactone, and PC.²⁴⁶

Poly(glycolic-co-lactic acid) (PLGA) and poly(ε-caprolactone) microspheres were produced under ambient conditions using one-step electrohydrodynamic jetting (atomisation) and TIPS in DMC. The presence of DMC generated microspheres with a diameter in the range of 150–300 μm, suitable for use in a minimally invasive, in situ forming scaffolds.²⁴⁷

7.3 Polyamide membranes

Another example of OCs as green solvents in membrane preparation was presented by Shi and co-workers, in which DMC and tannic acid (TA) were used to prepare high-performance polyamide (PA) reverse osmosis (RO) membranes. RO membranes are used to separate low molecular weight solutes, i.e., inorganic salts or small organic molecules, from a solvent.²⁴⁸ Therefore, these membranes have been applied in the purification of water (desalination) and in the concentration step in the food industry (concentration of fruit juice, sugar, coffee), and the dairy industry (concentration of milk prior to cheese manufacture).²³⁸

The characterization of the membrane achieved from TA showed that the presence of DMC changed the membrane structure, creating a more pronounced leaf-like architecture, thus demonstrating the significant contribution of the solvent in the final membrane morphology and characteristics. TA and DMC endowed the RO membranes with a high flux and a high salt rejection (99.03% ± 0.02%).²⁴⁸ DMC can also be used as a co-solvent to modify the interfacial polymerization (IP) process of polyamide membranes. The DMC-modified membrane rejection improved, while maintaining an excellent flux.²⁴⁹

In addition, DMC promoted the miscibility of aqueous and organic phases, thus enhancing the diffusion rate of m-phenylenediamine (MPD) from the aqueous phase into the organic phase. The accelerated diffusion of MPD due to DMC affected the structures and performance of the RO membrane, i.e., increasing the overall thickness of their skin layer.²⁴⁸

7.4 Polycarbonate membranes

Poly(trimethylene carbonate)-dimethylamine (PTMC-dMA) porous membrane-based scaffolds were produced via air–water interfacial phase separation using PC as the swelling agent. The formed membrane can find possible applications in tissue engineering.²⁵⁰

7.5 Cellulose acetate membranes

The formation of cellulose acetate nanofibers via electrospinning was performed using DMC and cyclopentanone (CPO) as the solvent system. The solvent composition affected the fibre diameter, morphology and porosity. DMC, due to its higher volatility, was responsible for pore formation.²⁵¹

7.6 Ion-exchange membranes

Ion exchange membranes made of highly porous polytriazole and functionalized with sulfonic acid were prepared by solution casting, followed by immersion in a non-solvent bath and applied for selective protein adsorption using a mixture of 1-ethyl-3-methylimidazolium acetate ([C₂mim]OAc) and DMC as the medium.²⁵² These types of membranes may be useful for protein separation and purification, offering higher flow rates compared to chromatographic techniques, and thus reducing the processing time.²⁵²

7.7 Ionomer membranes

EC was used in combination with sulfolane (SL) as a plasticizer to produce lithiated Nafion ionomer membranes, applicable both as electrolytes and separators. The conductivity of these membranes saturated with EC/SL is promising for various practical applications such as a polymer electrolyte in the development of a new generation of lithium-ion batteries with enhanced safety.²⁵³

7.8 Poly(hydroxybutyrate)-based membranes

Papchenko et al. compared several solvents for the casting of a poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) random copolymer-based membrane with potential applications in gas separation and CO₂ capture.²⁵⁴ Among them, DMC allowed the production of polymer films with transport properties similar to that obtained with chloroform, and it also led to stable crystallinity in the samples over time.²⁵⁴ These results demonstrate that DMC is a green alternative to CHCl₃ without compromising the separation performance.²⁵⁴

8. Organic carbonates in the preparation of materials and nanoparticles

OCs have shown interesting proprieties as polar media for the preparation of materials and nanoparticles and the substitution of DMF, NMP and DMSO.²⁵⁵

DMC was employed as the solvent for the fabrication of 3D porous PLGA-biomimetic carbonated apatite composite scaffolds,²⁵⁶ the liquid phase exfoliation (LPE) of pristine biochars as a substitute for NMP,²⁵⁷ in the production of porous alumina ceramics²⁵⁸ and in debinding assistance in stereolithography-based 3D-printed alumina green bodies.²⁵⁹ The latter materials subsequently underwent thermal debinding and sintering to obtain alumina ceramics. The application of DMC in this process was shown to positively affect the microstructure and properties of the 3D-printed alumina ceramics.²⁵⁹ The obtained materials could be used as ceramic cores for hollow blades in aircraft engines.²⁵⁹

DMC, DEC and EMC have been applied as anti-solvents to improve the efficiency of quasi-two-dimensional (quasi-2D) perovskites²⁵⁹ and perovskite solar cells (PSCs).^260,261 The former compounds have been identified as promising emitters for the fabrication of high-efficiency blue PeLEDs. In particular, the residual DMC in the perovskite can impede the grain coarsening during the heating process and preserve a smaller grain size than that of the commonly used anti-solvent chloroform. Furthermore, its better miscibility with the precursor solvent (DMSO) and higher boiling point are beneficial to achieve a more homogeneous morphology.²⁶² Additionally, DMC solvent molecules have been shown to act as a template in the production of methylammonium (CH₃NH₃⁺ or MA)-based 2D Ruddlesden-Popper perovskites.²⁶³

The combination of PC as a binder and DMC as a solvent was employed for the development of an ultra-low-temperature co-fireable Li₂WO₄ substrate through the tape-casting technique. The sintered substrate displayed a relatively high thermal expansion coefficient (ca. 16 ppm °C⁻¹) and excellent microwave dielectric properties with a relative permittivity of 5.4 and a very low dielectric loss of 9.21 × 10⁻⁵ at 5 GHz, making it suitable for microelectronic applications.²⁶⁴

Grafting organic functionalities on inorganic supports is one of the most used methods for the preparation of composites. Although toluene usually is the solvent of choice for the grafting reaction, it can be substituted with greener media, i.e., (+)-α-pinene, (−)-β-pinene, DMC, (+)-limonene, and Me-THF, even if only in the latter case no residual solvent molecules could be detected.²⁶⁵

Highly porous biocompatible composites made of polycaprolactone (PCL) and 45S5 Bioglass (BG) were prepared via the solid–liquid phase separation method (SLPS) using either DMC or dioxane as the solvent. The mechanical properties of the resulting composite showed a dependence on the type of solvent used for its preparation. The composites prepared with dioxane showed enhanced stress at deformation and higher elastic modulus with respect to that prepared with DMC.²⁶⁶

Mixtures of castor oil (CO) and DMC were used as the media in a microfluidic-assisted solvent extraction process, resulting in the formation of hollow silica microspheres with a hole on their surface, showing potential application as catalyst supports, microreactors or capturers for cells.²⁶⁷ Increasing the DMC content led to the formation of filbert-like silica solid microspheres instead.²⁶⁷

PCL electrospun structures for tissue engineering were prepared using a combination of glacial acetic acid as the solvent and EC as a co-solvent. The concentration of EC in the mixture could influence the diameter of the ultrafine PCL fibres, which decreased with an increase in the EC concentration. Therefore, this stable and low toxic solution electrospinning system may provide a valid strategy in the field of tissue engineering.²⁶⁸

EC was also used to dissolve low molecular weight methacrylate end-functionalized polymers, i.e., poly(trimethylene carbonate-dimethacrylate), poly(D,L-lactide-dimethacrylate), and poly(ethylene glycol-dimethacrylate), to produce porous crosslinked polymer networks applicable in the biomedical field.²⁶⁹

EC, PC and GC were shown to be optimal for the repulsive osmotic delamination of 2D materials as alternatives to N-methylformamide and N-methylacetamide.²⁷⁰ This technique is useful to achieve delamination into monolayers of ionic-layered compounds with quantitative yield.²⁷⁰

Concerning the production of nanomaterials, ruthenium nanoparticles could be deposited on thermally reduced graphite oxide using PC. These Ru@graphene nanomaterials acted as active catalysts for the solvent-free hydrogenation of benzene to cyclohexane under mild conditions (100 °C, 10 bar) with activity of 34 000 (mol cyclohexane) (mol Ru)⁻¹ (h⁻¹) and over 90% conversion in at least ten consecutive runs.²⁷¹ Additionally, esterified cellulose nanocrystals could be obtained by solution blow spinning (SBS) using DMC as the solvent.²⁷²

Finally, a two-dimensional titanium carbide (Ti₃C₂T_x) MXene was effectively dispersed in PC, expanding the opportunities for processing techniques, such as mixing MXenes with other nanomaterials or polymers to form composites and preparing inks for printing.²⁵⁵

GC can be used as a suitable green solvent for the synthesis of metal–organic frameworks (MOFs). In particular, Itatani and co-workers reported the synthesis of a zinc-based zeolitic imidazolate framework-8 (ZIF-8) using GC, which could then be recycled and reused for several cycles.²⁷³

9. Organic carbonates in surface modification

The enhanced molecular transport together with the good dissolution proprieties of PC makes it a suitable solvent for the preparation of alcohol-based monolayers on the surface of silicon oxides.²⁷⁴ Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. This strategy can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.²⁷⁴ Similarly, the surface modification of smectites was performed using five-membered cyclic OCs, i.e., GC, 4-(2-hydroxyethyl)-1,3-dioxolan-2-one (HED), 4-(4-hydroxybutyl)-1,3-dioxolan-2-one (HBD), 4-((benzyloxy)methyl)-1,3-dioxolan-2-one (BMD), and 4′-(oxybis(methylene))bis(1,3-dioxolan-2-one) (OMD) and hexahydrobenzo[d][1,3]dioxol-2-one (HDD), as the media (Fig. 4).⁷⁹

Fig. 4 Cyclic OCs employed as media for the surface modification of smectites.

DMC and EC–PC mixtures were found to be promising solvents for the adsorption of the dye Bixin onto acid- and alkali-treated kaolinite²⁷⁵ and for the adsorption of triblock Pluronic surfactants bearing poly(ethylene oxide) (PEO) chains of different lengths on silica.²⁷⁶

10. Organic carbonates as extracting solvents

Several examples of OCs employed as extracting solvents in a wide variety of applications are available in the literature including liquefaction processes, compound recovery and the determination of pollutants. In the latter case, dispersive liquid–liquid microextraction (DLLME) for the determination of lead content in water was performed using DMC as the extraction solvent.²⁷⁷ The analysis of DMC extracts was also used for the determination of the volatile fatty acid (VFA) concentration in digestates.²⁷⁸ In addition, DEC in combination with ionic liquids showed enhanced performances for the determination of metallic impurities in Arnica montana L. infusions via DLLME.²⁷⁹ DEC can be also used as an extractant for the analysis of highly substituted hydrophobic chlorophenols in wines using liquid-phase microextraction (LPME) and capillary electrophoresis (CE).²⁸⁰

10.1 Organic carbonates in liquefaction processes

Pinewood shaves could be liquefied using PC and GC as substitutes for 2-ethylhexanol with a biomass conversion of 96%, 98% and 71%, respectively. The bio-oils obtained led to significantly better calorific properties than that from the biomass itself.²⁸¹ Alternatively, the liquefaction of recycled newspaper can be carried out in the presence of polyhydric alcohols and EC under acidic conditions.²⁸²

10.2 Organic carbonates in the extraction of oils and fatty acids

DMC was employed in the extraction of diglycerides (DAGs) and free fatty acids (FFAs) from salmon oil²⁸³ and of kernel oils from Litsea cubeba (LC).²⁸⁴ In the latter case, DMC displayed enhanced performances compared to alcoholic solvents (yield values ca. 96%) and with values similar to n-hexane (ca. 96% yield). In addition, the micronutrients in oils extracted by these green solvents were quantified to be much higher than that extracted by n-hexane.²⁸⁴ DMC can also be employed as kernel oil extracting solvent through a controllable blender extractor (CBE).²⁸⁵

The application of DMC and DMC–EtOH mixtures as solvents in the pressurized liquid extraction (PLE) of Crambe seed oil showed greater oil removal from the seeds under pressurized conditions.^286,287

Tommasi and co-workers developed a new lipid extraction protocol for obtaining a fatty-acid-rich extract from the diatom Phaeodactylum tricornutum.²⁸⁸ Choline chloride-based deep eutectic solvents (DESs) and microwave (MW) pretreatments combined with DMC and scCO₂ as the extraction solvents resulted in an increase both the selectivity and the total fatty acid (TFA) extraction yield of DMC. In particular, the TFA yield and fatty acid profile results were comparable to that of the traditional Bligh and Dyer extraction method²⁸⁹ with a much better selectivity (88% vs. 35%). This pretreatment was also demonstrated to significantly improve the extraction efficiency of scCO₂, increasing the TFA yield by a factor of 20 and providing highly purified triglyceride extracts.²⁸⁸ In addition, milk fat extraction could be performed from ghee residue using DMC as the solvent.²⁹⁰

An ultrasonic-microwave-assisted extraction (UMAE) method with DMC was developed for the extraction of Manchurian walnut kernel oil (MWKO) with a maximum extraction yield of 59%.²⁹¹

10.3 Organic carbonates for the recovery of compounds

EC, PC and DMC were shown to be suitable media for the recovery of polyhydroxybutyrate (PHB), biosynthesized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)²⁹² and polyhydroxyalkanoates (PHA) from municipal waste activated sludge.^293–295 The same solvents could be used to recover PHA from the bacterial cytoplasm, i.e., Cupriavidus necator cells,^296–298 genetically modified E. coli cell cultures²⁹⁹ and from mixed microbial cultures.^300–303 With genetically modified E. coli cell cultures, the PHB yield values from DMC-based extraction were similar to or higher than that achieved using chloroform (≥67%).²⁹⁹ Particularly, EC-assisted PHB extraction from Cupriavidus necator cells was obtained with a recovery percentage of 98% and product purity up to 98%, which were the highest among the solvents tested (DMSO, DMF, hexane, propanol, methanol, and acetic acid).²⁹⁷

EC was also tested for the industrial separation of acetone and diisopropyl ether employing extractive distillation, even if DL-limonene showed higher performances.³⁰⁴

Acidified GC and EC can be useful for the pretreatment of sugarcane bagasse with a glucose yield of 80% and 15%, respectively.³⁰⁵ The usage of GC is also preferred because its decomposition produces glycerol, while EC generates EG, which is generally harmful.³⁰⁶

PC was found to be a suitable solvent for the isolation of PO during the epoxidation of propylene³⁰⁷ and for the extraction of aromatics in naphtha.^308–311 Specifically, a mixture of PC and diethylene glycol as the solvent system led to an increase in the utilization efficiency of naphtha,³¹¹ while DMC/n-butyl acetate mixtures were used as extracting media for the separation of coal gasification tar residue (CGTR).³¹² PC and BC were also used for the extraction of artemisinin from A. annua with high efficiency (90%–95%).³¹³

DMC could be also used to extract β-carotene from Rhodotorula glutinis yeast,³¹⁴ 6-methoxypodophyllotoxin from Linum tissues via ultrasound-assisted extraction³¹⁵ and peroxidase from bitter gourd (Momordica charantia); the latter one via a three-phase partitioning technique, yielding a peroxidase recovery and fold purity of 177% and 4.84, respectively.³¹⁶

DMC-based binary azeotropic mixtures showed good performances according to a computer-aided product design in extracting volatile aroma molecules widely used in the perfume and cosmetic industries, i.e., α-pinene, DL-limonene, α-terpinene, terpinolene, and many more.³¹⁷

DMC has been applied as extracting media for the biomonitoring of nicotine in aqueous samples³¹⁸ and it can be employed as a precipitating agent to isolate lignin from rice straws with 89% purity after a fractionation step.³¹⁹

Finally, a three-phase partitioning system with DMC as the organic phase and sodium citrate as the salt phase was used for the partitioning of exopolysaccharide (EPS), namely, EPS-D, from fermentation broth of Phellinus baumii. This procedure could also be applied for the efficient partitioning of natural biomolecules.³²⁰

DEC was positively tested as a possible entrainer for separating 1-hexene and n-hexane by extractive distillation,³²¹ as well as a green extraction solvent for the recovery of gold(III) from copper-rich sources³²² and chlorophenol determination in water samples with dispersive liquid–liquid microextraction.³²³ In the latter application, DEC can be employed as a substitute for more toxic or hazardous solvents i.e., hexane, chloroform, toluene and diethyl ether.³²³

In addition, DEC can be employed as a solvent for the determination of polycyclic aromatic hydrocarbons (PAHs) in different environmental matrices through GC–MS.³²⁴

Mixtures of water, propionic acid and DEC can be used for the recovery of propionic acid from aqueous solutions, i.e., fermentation broth and wastewaters.³²⁵

11. Organic carbonates in analytical chemistry

DMC as well as mixtures of PC and ethanol were effectively employed as the eluent phase in inductively coupled plasma mass spectrometry (ICPMS),³²⁶ HPLC³²⁷ and liquid chromatography,³²⁸ respectively. Mixtures of PC and ethanol may be considered a greener approach for pharmaceutical applications compared to CH₃CN. This replacement is achievable without any major compromise in terms of elution order, chromatographic retention, efficiency and peak symmetry, even if due to the reduced mass transfer of analytes in PC-based mobile phases, the optimal flow rates (necessary for reaching the maximum efficiency) are lower compared to CH₃CN-based mobile phases.³²⁸ Concerning ICPMS applications, the employment of DMC may facilitate the elution and detection of novel hydrophobic compounds and improve the column recovery under standard ICPMS conditions and instrumental set-up without a compromise in the detection limits.³²⁶

An assay method incorporating PC as the solvent was also developed to determine chlorthalidone (CLD) and cilnidipine (CIL) in bulk and tablet dosage form using four different UV spectrophotometric methods. Due to the solubility of most drugs in PC, this method can be adapted for the analysis of CIL and CLD drugs and it can be adopted by quality departments for regular research and sustainable development.³²⁹

In another example, the addition of supercharging reagents, i.e., PC, EC and BC, in electrospray ionization coupled mass spectrometry (ESI-MS) was demonstrated to increase the protein ion charge as well as narrow the protein charge-state distributions without impacting the obtained drug-to-antibody (DAR) values.^330–332 Particularly, 5% (v/v) concentration of BC and 4-vinyl-1,3-dioxolan-2-one could be added to ESI solutions to form higher charge states of cytochrome c and myoglobin ions than by using more traditional additives i.e., sulfolane and m-nitrobenzyl alcohol.³³¹

DMC was also used as an eluent for the chromatographic purification of a 10-amino acid-long peptide (purity of 98.5%)³³³ and for the separation of two small molecules, i.e., caffeine and paracetamol.³³⁴ The results indicated that a small amount (7% v/v) of DMC has the same efficiency as a 2.5-times larger volume of CH₃CN (18% v/v), and higher efficiency than alcohols, i.e., ethanol and isopropanol, in small molecule separation.³³⁴

12. Organic carbonates in biological/biochemical applications

Linear and cyclic OCs have been employed in some interesting applications as media in biochemical processes and assays. EC was shown to be an appealing alternative to formamide and formaldehyde in fluorescence in situ hybridization (FISH) designed for double-stranded DNA probes in plants. Adding EC to the hybridization solution not only allowed successful overnight hybridization but also enabled the possibility to reduce the hybridization time. The method was reproducible in all the DNA of the plants studied (Allium, Nigella, Tradescantia, and Vicia), giving a positive stimulus for improving gene-mapping approaches in plants.³³⁵

PC was employed as the medium for a colorimetric pyrophosphate assay used for the determination of the P₂O₇⁴⁻ anionic species (PPi) and based on the formation and reduction of the 18-molybdopyrophosphate ([(P₂O₇)Mo₁₈O₅₄]⁴⁻) anion. This process decreased the interference by ATP and prevented the yellow coloration of the reducing agent (ascorbic acid) due to the presence of excess Mo(VI) species. Thus, this method was shown to be useful for the assay of AMP + PPi forming enzymes, including adenylation enzymes.³³⁶

Solvent systems composed of isosorbide dimethyl ether and PC (also with DMSO in some cases) were used to prepare oral non-steroidal anti-inflammatory drugs (NSAIDs). These compounds have applications in the management of inflammatory diseases, including arthritis, bursitis and tendonitis.³³⁷ On this topic, PC and other moderately hydrophobic solvents in combination with phase-sensitive polymers can be utilized for modifying drug release from injectable implant systems for 21 days.³³⁸

Finally, the enzyme-catalysed transesterification of ethyl butyrate with n-butanol^339,340 and microalgae biomass (Scenedesmus sp.) to produce bioethanol and biodiesel³⁴¹ was performed using GC and DMC as the solvent, respectively.

12.1 Solid-phase peptide synthesis (SPPS)

Researchers are focused on the development of greener protocols for the production of pharmaceutical-grade peptides via solid-phase peptide synthesis (SPPS) by introducing more sustainable alternatives to the most common reagents and solvents.³⁴² On this topic, Ferrazzano and co-workers demonstrated that the traditional DMF-based protocol for industrial fluorenylmethoxycarbonyl (Fmoc) SPPS could be replaced by a greener one using combinations of Cyrene, sulfolane, or anisole with DMC or DEC, in different proportions.³⁴³ This method showed applicability for a wide range of oligopeptides, i.e., Aib-enkephalin and Aib-ACP. Finally, this procedure was applied to the synthesis of the reduced form of the active pharmaceutical ingredient (API) octreotide, isolating it in comparable yield and purity compared to that obtained with DMF.³⁴³

Also, the deprotection of the Fmoc group can be performed in a sustainable way by employing 3-(diethylamino)propylamine (DEAPA) as an alternative to piperidine in an N-octyl pyrrolidone/DMC 8 : 2 v/v solvent system. DMC allowed a decrease in solvent viscosity, making this mixture suitable for the automated solid-phase protocol.³⁴⁴ This approach was proven to be able to minimize the formation of side products, while achieving comparable results to that obtained with piperidine.³⁴²

13. Organic carbonates in cultural heritage

Several investigations aimed to replace toxic solvents with greener ones in different aspects of cultural heritage preservation and restoration, i.e., old varnishes, paints and tape removal.³⁴⁵

For instance, the cleaning of wax-based coatings applied on indoor 1460s bronzes was performed with a gel made by PHB as a thickening agent, biodiesel and DMC. DMC acts as a solubilizing agent for PHB, forming a jelly phase. This gel was then applied for the removal of fresh and aged beeswax coatings, avoiding problems related to solvent residues and ensuring safety for the artworks, the operators and the environment.³⁴⁶ The polymeric gel poly(ethylmethacrylate)-diethylcarbonate (PEMA-DEC) was also able to remove pressure-sensitive tape (PST) components without damaging the painting underneath.^347,348

Graffiti and mural removal from historic buildings, masonries and stone artworks can be achieved with a series of two-component systems, which combines silica sol–gel chemistry and DMC as a green solvent to be loaded into the gel. The efficiency of this system in adsorbing/trapping commercial red aerosol spray paint from Istrian stones was investigated, showing to be a promising cleaning agent.³⁴⁹ Moreover, DMC was also studied as a swelling solvent to produce thiol–ene photocured organogels by combining five different thiol or allyl functionalized bio-based monomers, namely isosorbide, pyrogallol, and limonene. The DMC swollen gels were found to be effective in removing the varnish from the surface of artwork, while avoiding adhesion to the surface layer of paintings,³⁵⁰ while DMC alone was employed for the removal of thermally aged oil-painted mock-ups.³⁵¹

A ternary mixture of water, PC and C9-11E6 (a non-ionic alcohol ethoxylate surfactant) was employed for the dewetting of a methacrylate/acrylate co-polymer film. The surfactant favours the loss of adhesion of the polymer, which may be found on works of art because of previous restoration interventions, thus needing to be removed.³⁵²

PC was also employed as a green medium in magnetic nano gel microemulsions, providing a drastic improvement in the cleaning efficiency of archaeological cartonnage.³⁵³

Finally, PC, DMC, DEC and DBC were used in combination with a biodegradable non-ionic surfactant in water to formulate a novel nanostructured cleaning system. This system was loaded in highly retentive hydrogels and effectively applied in the selective removal of over-paintings from laboratory mock-ups and from real pieces of street art.³⁵⁴

14. Organic carbonates as cleaning co-solvents

OCs were demonstrated to be excellent co-solvents as cleaning and de-painting products for carpets, rugs, and fabrics. PC can be used as a sequestering agent in environmentally benign cleaning formulations.³⁵⁵ In high concentrations (up to 25%), PC can be employed as a solvent for cleaning processes involving human contact.³⁵⁶ With its softening and swelling effect on paint, PC was found to be an appropriate solvent in aqueous mixtures for the removal of paints from skin. In this application, it was added as a co-solvent in up to 40%.³⁵⁷

The U.S. EPA evaluated the use of PC as a solvent in de-painting operations in air logistics centres.³⁵⁸ Furthermore, alkylene carbonates can be used to reduce the odor of amine-containing compounds such as urine. An advantage is the high biodegradability of OCs. Therefore, odor-reducing agents containing EC, PC or BC can be applied in open environments such as zoos, wool plants, and fish canneries.³⁵⁹ The reduction in odor is achieved by reaction of the respective carbonate with the amine. Furthermore, DACs such as GC are starting materials to synthesize non-ionic surfactants, which can be used in cleaning products.³⁶⁰

15. Organic carbonates in cosmetics and as sunscreen

Examples of DACs displaying long alkyl chains employed in cosmetics can be found in the literature; most of them are reported in patented formulations.

Natural make-up primers were prepared using dioctyl carbonate (DOC) as the oil phase solvent, in which plant and mineral-derived compounds are dissolved.³⁶¹ DOC was applied as an emollient in anhydrous cosmetic sunscreens together with diisopropyl sebacate, isononyl isononanoate and diisopropyl adipate, a UV filter system and silicone blends (selected from the group of dimethicone, dimethicone/vinyl dimethicone co-polymer and polydimethyl siloxane). The obtained cosmetic sunscreen displayed enhanced stability and provided a high sun protection factor (SPF).³⁶² The emollients (namely, alkyl benzoate, dibutyl adipate, caprylic/capric triglyceride, coco-caprylate, isopropyl myristate and dioctyl carbonate) showed impact on the UV-filter performances in terms of the SPF and UVB protection, while the UVA shielding decreased with a decrease in the emollient polarity (dicapryl carbonate being the least polar). Therefore, polar emollients are advocated to optimize the UVA protection.^363,364

16. Organic carbonates in varnish and paints

OCs can be used for the dispersion of nonaqueous liquid pigments due to their high boiling and flash points.³⁶⁵ Usually, 50–75 wt% of the chemicals in the lacquer wire-coating process are organic solvents. In particular, thin wires need a higher amount of organic solvents. In addition, cresol could be replaced by PC after the comparison of the complete life cycle of both solvents including production, application, and waste removal in the copper wire-coating process.³⁶⁶

Opportunely modified OCs have been employed in new water-based varnish formulations.³⁶⁷ Among the OCs tested, 2-(2-methoxyethoxy)ethyl methyl carbonate (DGlyMC) was found to be the best one in terms of toxicological evaluation.³⁶⁷

17. Organic carbonates in coatings

Miller et al. investigated the use of paint blends thinned by mixtures of DMC and tert-butylbenzene to create low-stress films to be used as solar absorber coatings. These coatings exhibited a strong optical performance with figure of merit (FOM) and solar absorbance values of 91% and 97%, respectively, making them ideal coatings for next-generation concentrated solar power plants.³⁶⁸ The utilization of these solvents also helps reducing the environmental impact of paints, specifically by decreasing the VOC content and MIR value to 395 g L⁻¹ and 1.04, respectively.³⁶⁸ PC was also tested for the solution-processable deposition of CuSCN as the hole transport layer (HTL) in bulk heterojunction solar cells, although with lower efficiencies compared to DMF and DMSO (2.5%, 4.5% and 4.2%, respectively).³⁶⁹

18. Organic carbonates in oil and natural gas processing industry

The FLUOR process is one of the oldest industrial applications of OCs (especially PC). This process uses PC as a physical solvent to remove CO₂ and H₂S. PC also removes C₂₊ hydrocarbons, COS, SO₂, CS₂, and H₂O from the natural gas stream.³⁷⁰ In fact, PC has an equilibrium capacity for absorbing carbon dioxide several times higher than water and does not absorb high amounts of natural gas and hydrogen. Owing to its low viscosity, low vapor pressure, and noncorrosive behaviour, it is an excellent choice as an absorbing solvent.³⁷¹

Other cyclic OCs, namely EC, PC, BC, hexylene carbonate (HexC), cyclohexene carbonate (CHexC), styrene carbonate (SC), GC and (chloromethyl)ethylene carbonate (CEC), were applied as substitutes for sulfolane to mitigate the residual aromatic content (dearomatization, desulfurization and denitrogenation) in liquid fuels.³⁷² Among them PC, EC, BC and SC showed competitive results compared to sulfolane, with PC providing a promising process performance at a very competitive solvent to feed (S/F) ratio and specific energy consumption.³⁷²

19. Organic carbonates and electronics

PC can be used as the solvent in the formation process of alignment films for the development of liquid crystal devices. It is necessary that the solvent can be modified by a second solvent to control the surface tension during the process.³⁷³ It was found that PC can be used in both functions, with the best results obtained in combination with glycol ethers. Organic carbonates can be also used for the fabrication of sensors, i.e., a PC-based ammonia sensor was developed.³⁷⁴

Furthermore, PC was demonstrated to be an excellent solvent for capillary electrophoresis for the investigation of the mobility and ionization constants of various aliphatic amines.³⁷⁵ This technique allows the separation of ionic compounds based on their electrophoretic mobility, which is dependent on the charge, viscosity and radius of the ions involved.³⁷⁶

The detection of thallium(III) and other inorganic salts has been accomplished by polarographic methods in PC as part of extractive mixtures with water³⁷⁷ for ‘salting-out’ extractions.³⁷⁸ Finally, neutral substances such as phenanthrene could be separated by nonaqueous capillary electrophoresis using cationic additives in PC.³⁷⁹

20. Organic carbonates as electrolytes

20.1 Organic carbonates in lithium batteries

The development of rechargeable lithium batteries based on electrolyte solvents is considered a milestone in the field of energy storage and supply for electrical and electronic devices (Fig. 5).^380,381

Fig. 5 OCs as electrolytes in lithium-ion batteries.

The role of electrolytes in batteries is to serve as the medium for the transfer of charges, which are in the form of ions, between a pair of electrodes.

In lithium-ion batteries, lithium ions are solvated by an organic solvent and they diffuse freely between the two half-cells (anode and cathode compartments), which are physically isolated from each other by a separator membrane.^382–384 Thus, an ideal electrolyte solvent must have a high dielectric constant to dissolve a high electrolyte salt concentration, have low viscosity to facilitate ion transport, be chemically inert to all cell components to improve the battery lifetime, be liquid over a wide temperature range (i.e., have low melting point and high boiling point), and have low flammability (high flash point).³⁸⁵

Thus, PC is considered the preferred electrolyte in lithium batteries due to its wide liquid range, high dielectric constant and static stability with lithium. Mixtures of EC and PC are considered the most suitable solvent system for common lithium salts to be used as the electrolyte liquid carrier in lithium-ion batteries^386–390 as well as EC and EMC blends,³⁹¹ thus representing a standard for the evaluation of new salts and electrochemical systems.^392–395

On this matter, general investigations on the conductivity of organic electrolyte solutions were published by Petrowsky et al.³⁹⁶ The mass transport and conductivity in DAC electrolytes (PC, EC, and DEC and mixture thereof) were determined for LiClO₄,³⁹⁷ KPF₆ and LiPF₆,³⁹⁸ and for LiBr in mixtures with iodine.³⁹⁹

EC and PC can be also combined with other compounds, i.e., lithium(fluorosulfonyl)(trifluoromethanesulfonyl)imide (LiFTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), to improve the stability and safety of Li-ion batteries^400–402 or with deep eutectic solvents (DES), such as choline chloride/ethylene glycol and choline chloride/malonic acid, to improve the thermodynamic and transport proprieties of LiNO₃.⁴⁰³

In addition, DMC is finding increasing application as a non-aqueous electrolyte component in the field of lithium rechargeable batteries, as attested by the number of patents in this area.^46,62,404 Hybrid aqueous-DMC electrolytes were also reported.⁴⁰⁵

Moreover, GC has a higher dielectric constant compared to other carbonate solvents used in lithium cell electrolytes. This enables larger quantities of Li salts, i.e., LiF₂BC₂O₄, LiPF₆, LiBF₄ and/or LiB(C₂O₄)₂, to be dissolved in GC.⁴⁰⁶

Finally, non-polar electrolyte solvents such as DMC and EMC can be selectively extracted from spent Li-ion batteries using sub-critical or scCO₂, while the recovery of the polar EC seems to be more challenging.⁴⁰⁷ However, through a low temperature thermal treatment process (<150 °C), EC can also be successfully recovered.⁴⁰⁸

20.2 Fluorinated organic carbonates as electrolytes

Fluorinated DACs, such as fluoroethylene carbonate (FEC),^409–412 monofluoroethyl methyl carbonate (F₁EMC), difluoroethyl methyl carbonate (F₂EMC), methyl (2,2,2-trifluoroethyl) carbonate (F₃EMC),^413,414 bis(2,2,2-trifluoroethyl) carbonate (BTFC),⁴¹⁵ trifluoropropylene carbonate (TFPC) and their mixtures,⁴¹⁶ have been extensively studied as electrolytes. These compounds showed promising performances (i) as high-voltage electrolytes for Li-ion batteries,^417–419 (ii) for localized high concentration electrolytes (LHCE),⁴²⁰ (iii) to make highly concentrated electrolyte solutions for Si nano-flake powder negative electrodes⁴²¹ and (iv) for enabling long-term operation of Li-metal batteries at low temperatures.⁴²²

FEC was also added to the classical electrolyte mixture of EC and EMC to improve the thermal properties of the solid electrolyte interphases (SEI).⁴²³ FEC has been applied as a co-solvent in sodium metal anodes (SMEs), overcoming the low reversibility of SMEs in carbonate-based electrolytes.⁴²⁴

Furthermore, better cathode performances were noted when vinylene carbonate (VC) was added to an electrolyte EC solution.^425–428

One major problem for all organic solvent electrolytes is their flammability. This problem can be overcome by adding F₃EMC^429–431 or tris(2-chloropropyl) phosphate⁴³² to the electrolyte, although this flame-retardant characteristic affects the viscosity and capacity ratio during discharge.⁴³³ Other studies evaluated the use of fluorinated ionic liquids and DMC as a co-solvent.⁴³⁴

20.3 Organic carbonates as electrolytes in other applications

Cyclic DACs were employed as media in the electrocatalytic reduction of 1,3-dibromopropane (DB3) at metallic interfaces such as Au, Pt, Pd, and Rh.⁴³⁵ This process permits both the dissolution of precious metals and their deposition onto glassy carbon and graphite, applicable for the fabrication of composite materials.⁴³⁵ Moreover, the mechanical properties of the SEI can be improved by polymer species generated from solvent decomposition, i.e., EC, PC, DEC, FEC and VC.^436–439

VC has also been shown to decrease the formation of potentially toxic organofluorophosphates (OFPs) within the electrolyte during cycling at conventional upper cut-off voltages (UCVs), while triggering OFP formation at higher UCVs.⁴⁴⁰ Moreover, VC has been applied as a filmogen to realize a stable solid–solid cyclic process in lithium–sulfur batteries (LSBs).⁴⁴¹

EC/DEC blends, in the presence of potassium salts, resulted in superior cycling stability and kinetic performance of a hard carbon (HC) anode in potassium-ion batteries (PIBs).⁴⁴² EC has been shown to stabilize DEC by weak intermolecular interactions, enhancing the energy difference between the orbitals of the Li⁺(EC)_x(DEC)_y complex, demonstrating strong capability against reduction.⁴⁴³ LiPF₆-methyl acetate/DEC solution systems can be applied as electrolytes in dual-ion batteries.⁴⁴⁴ Dimethyl dicarbonate (DMDC)⁴⁴⁵ as well as mixtures of DMC and co-solvents such as PC, 1,1,1,3,3-pentafluorobutane (PFB) and other fluorinated aromatic hydrocarbons have also been investigated.^446–448

A colloid liquid electrolyte (CLE) was designed using the EC/DMC solvent system and trace amounts of lithium thiocarbonate (LTC) colloids. This combination was shown to improve the Li⁺ transfer kinetics at the cathode/electrolyte interface.⁴⁴⁹

Additionally, gel polymer electrolyte (GPE) and solid polymer electrolyte (SPE) technologies use organic carbonates in combination with Li salts to obtain high conductivity, cohesion and adhesion.^450,451 An effective lithium–air GPE system could be applied with a 50% epoxidized natural rubber polymer with 35% LiCF₃SO₃ and 10% PC as a plasticizer. Employing different mixtures of EC or PC, lower conductivities were observed.⁴⁵² In contrast to a liquid electrolyte system of 1.0 M LiClO₄/PC, the polymer electrolyte was more stable against corrosion.⁴⁵³

Moreover, non-commercial OCs, i.e., bis(2-methoxyethyl) carbonate (Gly₂C)⁴⁵⁴ and chlorinated EMC showed promise as electrolytes, exhibiting considerable oxidative/reductive stability, relatively weak solvation ability and low flammability.^455,456

21. Other applications

In this section, we present the other applications of organic carbonates that were not discussed beforehand.

EC and PC were applied as solvents for the synthesis of dielectric gels with 2-ethylhexyl acrylate (2-EHA) and 4-acryloylmorpholine (ACMO) as polymer networks. The sensitivity of the capacitive sensor made of the new dielectric gel increased by about 6 times compared to the sensors made of VHB, polydimethylsiloxane (PDMS), or Ecoflex, making it suitable for application as the transparent cover layer of a cell phone.⁴⁵⁷

PC, EC and GC can be added to peroxide solutions to improve their stability over an accelerated aging period. This result can be exploited to improve the stability of ready-to-use disinfectants, regardless of the other the ingredients included in their formulations.⁴⁵⁸

Kupareva et al. investigated the removal of silicon and its chemical species from oil under alkaline conditions by adding DMC to the reaction mixture. DMC favoured the reduction of solid products in the reaction mixture, thus fostering the oil recycling process.⁴⁵⁹ According to Okamoto et al.,^460–462 the siloxane bond is efficiently cleaved with DMC over solid-base catalysts to afford methoxy-terminated linear siloxane and carbon dioxide.

Scanning electrochemical microscopy (SECM) used in the feedback mode is one of the most powerful versatile analytical tools used in the field of battery research. However, the application of SECM in the field of lithium-ion batteries (LIBs) faces challenges associated with the selection of a suitable redox mediator due to its high reactivity at low potentials at lithium metal or lithiated graphite electrodes. In this regard, the electrochemical/chemical stability of 2,5-di-tert-butyl-1,4-dimethoxybenzene (DBDMB) was evaluated and benchmarked with ferrocene. This investigation was systematically carried out in electrolytes containing both linear and cyclic OCs. Measurements of the bulk current with a microelectrode proved that while DBDMB decomposed in the EMC-containing electrolyte, the bulk current remained stable in the cyclic carbonates, EC and PC.

Ferrocene was studied as an alternative redox mediator, showing a superior electrochemical performance in EMC-containing electrolytes in terms of degradation.⁴⁶³

22. Conclusions and future perspectives

As stated above, to the best of our knowledge, this is the first review focusing on the application of OCs as media. In this view, herein we presented a comprehensive analysis of the applications of OCs as green solvents, progressing from lab-scale to industrial applications.

OCs are valued for their diverse physical and chemical properties, making them excellent alternatives not only in organic synthesis but also across a range of other applications. Research into the use of OCs as solvents has increased significantly over time (Fig. 6), reflecting the growing recognition of their potential within a sustainability framework.

Fig. 6 Number of reported scientific investigations employing OCs as solvents in organic synthesis (light blue) and as media for different applications (dark blue). Articles in which OCs were used as media for polymerization and depolymerization reactions were considered part of the organic synthesis group.

According to the analysis on the type of OCs employed, numerous works focused on the exploitation of commercially available DACs, i.e., DMC, EC and PC; however, many studies also focused on the development of custom-made OCs to meet the specific chemical and physical criteria required for a precise transformation. This trend opens exciting possibilities for new applications, given that these novel OCs can be synthesized in large quantities owing to mature synthetic methods.

Alternatively, it should be mentioned that despite the well-documented low toxicity and hazardousness of most OCs, a comprehensive evaluation of the greenness of their synthetic processes is still lacking. Although tools such as green metrics and life cycle assessments (LCA) are available, further research is needed on the end-of-life disposal and biodegradability of OCs to fully understand their environmental impact.

As highlighted in this review, OCs offer more than just a replacement for toxic solvents; they present an opportunity to revolutionize various scientific fields towards more sustainable practices. From improving the performance of batteries and advancing materials science to driving innovations in green chemistry and enhancing industrial sustainability, their potential is vast. The widespread adoption of OCs as green solvents is likely to have far-reaching effects, making them a valuable resource for researchers and industries focused on developing more sustainable processes.

Abbreviations

[C2mim]OAc	1-Ethyl-3-methylimidazolium acetate
2-EHA	2-Ethylhexyl acrylate
2-Me-THF	2-Methyl-tetrahydrofuran
2-Me-β-CD	2-O-Methylated B-cyclodextrin
4CzIPN	1,2,3,5-Tetrakis(carbazol-9-Yl)-4,6-dicyanobenzene
ACMO	4-Acryloylmorpholine
ADPS	3-((3-Aminopropyl)dimethylammonio) propane-1-sulfonate
API	Active pharmaceutical ingredient
ATRP	Atom transfer radical polymerization
BA	N-Butyl acrylate
BC	Butylene carbonate
BCB	4′-(Bromomethyl)-2-cyanobiphenyl
BMD	4-((Benzyloxy)methyl)-1,3-dioxolan-2-one
BPO	Benzoyl peroxide
BTF	Benzotrifluoride
BTFC	Bis(2,2,2-trifluoroethyl) carbonate
CAGR	Compound annual growth rate
CBE	Controllable blender extractor
CE	Capillary electrophoresis
CEC	(Chloromethyl)ethylene carbonate
CHexC	Cyclohexene carbonate
CIL	Cilnidipine
CIR	Cosmetic ingredient review
CL	E-caprolactone
CLD	Chlorthalidone
CLE	Colloid liquid electrolyte
CNTs	Carbon nanotubes
CO	Castor oil
CPME	Cyclopentyl methyl ether
CPO	Cyclopentanone
CPS	Chlorophosphonium salt
CyO	Cyclooctene
DA15C5	Diaza-15-crown-5
DAC	Dialkyl carbonate
DAGs	Diglycerides
DAllC	Diallyl carbonate
DAR	Drug-to-antibody
DB3	1,3-Dibromopropane
DBC	Dibutyl carbonate
DBDMB	Dimethoxybenzene
DCB	Dichlorobenzene
DCE	Dichloroethane
DCM	Dichloromethane
DEAPA	3-(Diethylamino)propylamine
DEC	Diethyl carbonate
DEPG	Dimethyl ethers Of polyethylene glycol
DES	Deep eutectic solvent
DETA	Diethylenetriamine
DGly2C	Bis(2-(2-methoxyethoxy)ethyl) carbonate
DGlyMC	2-(2-Methoxyethoxy)ethyl methyl carbonate
DHMF	2,5-Bis(hydroxymethyl)furan
DLLME	Dispersive liquid–liquid microextraction
DMA	Dimethyl acetamide
DMC	Dimethyl carbonate
DMDC	Dimethyl dicarbonate
DMF	Dimethyl formamide
DMI	Dimethyl Isosorbide
DMSO	Dimethyl sulfoxide
DOC	Dioctyl carbonate
DPC	Dipropyl carbonate
DPhC	Diphenyl carbonate
dppe	Bis(diphenylphosphino)ethane
EC	Ethylene carbonate
EG	Ethylene glycol
EGD	European green deal
EMC	Ethyl methyl carbonate
EMIMBr	1-Ethyl-3-methylimidazolium bromide
EO	Ethylene oxide
EPA	Environmental protection agency
EPS	Exopolysaccharide
ESI-MS	Electrospray ionization-coupled mass spectrometry
FDA	Food and drug administration
F1EMC	Monofluoroethyl methyl carbonate
F2EMC	Difluoroethyl methyl carbonate
F3EMC	Trifluoroethyl methyl carbonate
FEC	Fluoroethylene carbonate
FFAs	Free fatty acids
FISH	Fluorescence in situ hybridization
Fmoc	Fluorenylmethoxycarbonyl
FOM	Optical performance
GC	Glycerol carbonate
GCB	Glycerol carbonate butyrate
GCP	Glycerol carbonate propionate
Gly2C	Bis(2-methoxyethyl) carbonate
GPE	Gel polymer electrolyte
GVL	γ-Valerolactone
HBD	4-(4-Hydroxybutyl)-1,3-dioxolan-2-one
HBpin	Pinacolborane
HC	Hard carbon
HDD	Hexahydrobenzo[d][1,3]dioxol-2-one
HED	4-(2-Hydroxyethyl)-1,3-dioxolan-2-one
HexC	Hexylene carbonate
HMF	5-Hydroxymethyl Furfural
HMTA	Hexamethylenetetramine
HR	Hardwood residue
HTL	Hole transport layer
IBA	Isobutyraldehyde
iBuVE	Isobutyl vinyl ether
IBX	2-Iodoxybenzoic acid
ICPMS	Inductively coupled plasma mass spectrometry
ILs	Ionic liquids
ITO	Indium tin oxide
LC	Litsea cubeba
LEDs	Light emitting diodes
LHCE	Localized high concentration electrolytes
LIBs	Lithium-ion batteries
LiFSI	Lithium bis(fluorosulfonyl)imide
LiFTFSI	Lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide
LPE	Liquid phase exfoliation
LPME	Liquid-phase microextraction
LSBs	Lithium–sulfur batteries
LTC	Lithium thiocarbonate
MBP	Methyl 2-bromopropionate
MEA	2-Methoxy ethyl acrylate
MIAK	5-Methyl-2-hexanone
MIBK	Methyl isobutyl ketone
MOF	Metal–organic framework
MPD	m-Phenylenediamine
MPS	Methyl phenyl sulfide
MTAE	Methyl-tert-amyl ether
MTBE	Methyl tert-butyl ether
MTO	Methyltrioxorhenium
MW	Microwave
MWKO	Manchurian walnut kernel oil
NBA	N-Butylaniline
NBS	N-Bromosuccinimide
N-CNT	Nitrogen-doped carbon nanotubes
NHC	Nickel-N-heterocyclic carbene
NIPS	Non-solvent induced phase separation
NMA	N-Methylaniline
NMF	N-Methylformamide
NMP	N-Methyl pyrrolidone
NSAIDs	Non-steroidal anti-inflammatory drugs
OBMF	5,5′-[Oxybis(methylene)]bis-2-furfural
OC	Organic carbonate
OFPs	Organofluorophosphates
OL	Organosolv lignin
OMD	4′-(Oxybis(methylene))bis(1,3-dioxolan-2-one)
OSN	Organic solvent nanofiltration
PA	Polyamide
PAHs	Polycyclic aromatic hydrocarbons
PAN	Polyacrylonitrile
PC	Propylene carbonate
PCL	Polycaprolactone
PDMS	Polydimethylsiloxane
PEDOT	Poly(3,4-ethylenedioxythiophene)
PEF	Polyethylene furanoate
PEG	Polyethylene glycol
PEMA-DEC	Poly(ethylmethacrylate)-diethylcarbonate
PEO	Poly(ethylene oxide)
PES	Polyethersulphone
PET	Polyethylene terephthalate
PFB	Pentafluorobutane
PHA	Polyhydroxyalkanoates
PHB	Polyhydroxybutyrate
PHBV	Poly(hydroxybutyrate-co-hydroxyvalerate)
PIBs	Potassium-ion batteries
PIPOx	Poly(2-isopropyl-2-oxazoline)
PLA	Polylactic acid
PLE	Pressurized liquid extraction
PLGA	Poly(D,L-lactide-co-glycolide)
PMDETA	Cubr/N,N,N0,N0,N00-pentamethyldiethylenetriamine
PMDI	Poly4,4′-diphenyl methane diisocyanate
PO	Propylene oxide
PSCs	Perovskites solar cells
PST	Pressure sensitive tapes
PTC	Phase transfer catalysis
PTMC-dMA	Poly(trimethylene carbonate)-dimethylamine
PU	Polyurethane
PV	Pervaporation
PVDF	Polyvinilydene fluoride
RAFT/MADIX	Reversible addition–fragmentation chain transfer polymerization/macromolecular design via the interchange of xanthates
RCM	Ring-closing metathesis
RO	Reverse osmosis
SBS	Solution blow spinning
SC	Styrene carbonate
scCO2	Supercritical CO2
SECM	Scanning electrochemical microscopy
SEI	Solid electrolyte interphases
SET-LRP	Single electron transfer living radical polymerization
SFAME	Sunflower fatty acid methyl ester
SL	Sulfolane
SLPS	Solid–liquid phase separation method
SMEs	Sodium metal anodes
SPE	Solid polymer electrolyte
SPF	Sun protection factor
SPPS	Solid phase peptide synthesis
TA	Tannic acid
TDI	Toluene diisocyanate
TEAB	Tetraethylammonium bromide
TFA	Total fatty acid
TFC	Thin-film composite
TFE	Tetrafluoroethylene
TFPC	Trifluoropropylene carbonate
TIPS	Thermally induced phase separation
TMC	Trimethylene carbonate
TO	Tin oxide
UCVs	Upper cut-off voltages
UMAE	Ultrasonic-microwave-assisted extraction
VC	Vinylene carbonate
VDF	Vinylidene fluoride
VFAs	Volatile fatty acids
VIPS	Vapor induced phase separation
VOS	Volatile organic solvents
ZIF	Zinc-based zeolitic imidazolate framework

Author contributions

G. Trapasso: investigation, data curation, visualization, writing – original draft; F. Aricò: conceptualization, supervision, writing – review and editing.

Data availability

No primary research results, software or code have been included, and no new data were generated or analysed as part of this review.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the DoE 2023–2027 (MUR, AIS.DIP.ECCELLENZA2023_27.FF project).

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