Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study

Rehman, Abdul; Fernández, Alicia Calleja; Resul, M.F.M. Gunam; Harvey, Adam

doi:10.1016/j.jcou.2018.12.001

Cited by 53 publications

(31 citation statements)

References 82 publications

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“…This finding suggested cis ‐ 2 and trans ‐ 2 differ in their reactivity towards CO 2 insertion; an observation that has also been reported by Kleij and co‐workers recently . Indeed, considering conformational and steric effects of the double inversion pathway of halide‐catalysed CO 2 insertion (Figure ), it is clear that nucleophilic activation of cis ‐ 2 by halide (X − ) is less favourable than in the case of the more easily accessible trans ‐ 2 . Although we have not computed their thermodynamics, we expect the carbonate isomers cis ‐ 3 and trans ‐ 3 to be very close in energy, and thus propose the observed discrimination between cis ‐ 2 and trans ‐ 2 in the CO 2 insertion step to be kinetic in nature.…”

Section: Resultssupporting

confidence: 91%

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Maltby

Hutchby

Pluciński

et al. 2020

Chemistry A European J

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The selective catalytic synthesis of limonene‐derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol–ene addition and amine ring‐opening is reported. A phosphotungstate polyoxometalate catalyst used for limonene epoxidation in the 1,2‐position is shown to also be active in cyclic carbonate synthesis, allowing a two‐step, one‐pot synthesis without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double‐activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by‐product formation in commercial mixtures of 1,2‐limomene oxide. Carbonation of 8,9‐limonene epoxide furnished the 8,9‐limonene carbonate for the first time. Both cyclic carbonates underwent thiol–ene addition reactions to yield linked di‐monocarbonates, which can be used in linear non‐isocyanate polyurethanes synthesis, as shown by their facile ring‐opening with N‐hexylamine. Thus, the selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio‐based polymers.

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Section: Resultssupporting

confidence: 91%

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Maltby

Hutchby

Pluciński

et al. 2020

Chemistry A European J

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“…We subsequently focused on epoxidized polyunsaturated EFAEs bearing multiple epoxide moieties such as epoxidized methyl linoleate ( 1 f ) and epoxidized methyl linolenate ( 1 g ) that were prepared in cis ‐form from the corresponding fatty acids by epoxidation with m ‐CPBA . Carbonation of 1 f under standard optimized conditions (Table , entry 1), led to complete conversion of the starting material and formation of the desired carbonate product mostly with retention of cis configuration in the product.…”

Section: Resultsmentioning

confidence: 99%

“…Quaternary ammonium and phosphonium halide salts are active species for the cycloaddition of CO 2 to EFAEs and other internal epoxides. However, efficient use of such compounds as catalysts requires reaction temperatures above 120 °C, reaction times spanning over several days and high (≥40 bar) to very high (≈100 bar) CO 2 pressure. Addition of metal‐based Lewis acidic complexes to nucleophilic quaternary salts has the effect to strongly accelerate carbonation of internal epoxides; Fe(II) bispincer‐type, V(V) and Al(III) aminotriphenolate complexes were reported to promote the carbonation of epoxidized methyl oleate (EMO) in the 70–100 °C temperature range under 5–10 bar CO 2 in presence of nucleophilic halide salts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO₂ to Oleochemicals

2020

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Oleochemicals such as functionalized fatty acid esters and vegetable oils are classes of renewably sourced compounds that are increasingly attracting attention in sustainable chemistry as replacement for fossil-fuel based chemicals. The possibility of coupling CO 2 with epoxidized fatty acids esters (EFAEs) and epoxidized vegetable oils (EVOs) to afford compounds that are attractive as additives or chemical intermediates in the synthesis of non-isocyanate polyhydroxyurethanes (NIPU) can conjugate highly soughtafter CO 2 valorization with the exploitation of bio-based substrates. In this context, there have been very few attempts to employ organocatalytic hydrogen bond donors (HBDs) in the cycloaddition reaction of CO 2 to EFAEs and EVOs and no studies focusing on bio-based and readily available HBDs. In this work we show that ascorbic acid is an efficient HBD for the cycloaddition of CO 2 to EFAEs and EVOs under mild reaction conditions of temperature (80-100°C) and pressure (5-10 bar) that could be applied to several kinds of substrates (monounsaturated EFAEs, polyunsaturated EFAEs and EVOs). In all cases, the formed by-products (ketones, allylic alcohols, cyclic ethers etc.) were identified and the reaction conditions were tuned in order to obtain the target carbonates, generally, in high yields and selectivity.[a] W. Natongchai, S. Pornpraprom,

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“…It has a smell similar to orange and has been used to synthesize chemical materials in household cleansers and renewable energies. This hydrocarbon can be effectively oxidized in humid environments and may be a chiral particle [22].…”

Section: Ferula Asafoetida Constituentsmentioning

confidence: 99%

Antibacterial Effects of Green-Synthesized Silver Nanoparticles Using Ferula asafoetida against Acinetobacter baumannii Isolated from the Hospital Environment and Assessment of Their Cytotoxicity on the Human Cell Lines

Abootalebi

Mousavi

Hashemi

et al. 2021

Journal of Nanomaterials

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Acinetobacter baumannii (A. baumannii) is a dangerous nosocomial pathogen in intensive care units, causing fatal clinical challenges and mortality. In this study, the green synthesis of silver nanoparticles (AgNPs) using the extract of Ferula asafetida and the chemical synthesis of AgNPs were carried out to evaluate their effects on A. baumannii bacterial strain and a human adenocarcinoma cell line. The NPs were characterized using several techniques, including field emission-scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectrometry, UV-visible spectroscopy, and Fourier-transform infrared spectroscopy. After synthesis, the arrangement of AgNPs was confirmed based on the maximum absorption peak at 450 nm. The results showed that the AgNPs had a hexagonal structure. The antimicrobial activity of biogenic NPs significantly increased and reached a minimum inhibitory concentration of 2 μg/mL. The nanomaterials did not exhibit any toxic effects on the human cell line at certain concentrations and showed improvements compared to chemically synthesized AgNPs. However, at higher concentrations (100 μg/mL), the cytotoxicity increased. Finally, it was concluded that biosynthesized AgNPs had significant antimicrobial effects on A. baumannii isolated from intensive care units.

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Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study

Cited by 53 publications

References 82 publications

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO₂ to Oleochemicals

Antibacterial Effects of Green-Synthesized Silver Nanoparticles Using Ferula asafoetida against Acinetobacter baumannii Isolated from the Hospital Environment and Assessment of Their Cytotoxicity on the Human Cell Lines

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Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study

Cited by 53 publications

References 82 publications

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO2 to Oleochemicals

Antibacterial Effects of Green-Synthesized Silver Nanoparticles Using Ferula asafoetida against Acinetobacter baumannii Isolated from the Hospital Environment and Assessment of Their Cytotoxicity on the Human Cell Lines

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Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO₂ to Oleochemicals