A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

Mileghem, Seger Van; Borggraeve, Wim M. De; Baxendale, Ian R.

doi:10.1002/ceat.201800012

Cited by 19 publications

(16 citation statements)

References 60 publications

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“…- Basic resins such as Ambersep® 900 (hydroxide functional resin) filling glass column reactor in a continuous flow process. High glycerol conversion and reaction selectivity with a short residence time (10 min) are resulted from this process (Van Mileghem et al, 2018).…”

Section: Research Update On Gc Synthesismentioning

confidence: 99%

“…- Homogeneous ammonium catalysts: tetraethylammonium pipecolinate gives the best results in terms of glycerol conversion and reaction selectivity (Van Mileghem et al, 2018).…”

Section: Research Update On Gc Synthesismentioning

confidence: 99%

“…Different conversion routes for synthesis of glycerol carbonate (adapted from reference Van Mileghem et al, 2018). …”

Section: Introductionmentioning

confidence: 99%

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Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Bandres

Urrutigoı̈ty

et al. 2019

Front. Chem.

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The state of the art on the glycerol carbonate (GC) synthesis has been updated since the last published reviews in 2012, 2013, and 2016. Three types of reactions continue to be studied: glycerolysis of urea, transcarbonation of DMC, DEC, or cyclic carbonates with glycerol and reaction using CO 2 . Among these different routes, DMC and glycerol were selected as the raw materials for the GC synthesis in this work since the transcarbonation from these green reagents leads to high yields and selectivities, using mild conditions including a less energy consuming GC separation process. Catalytic conditions using Na 2 CO 3 seem to be a good compromise to achieve a high yield of GC, leading to an easier purification step without GC distillation. Mild temperatures for the reaction (73–78°C) as well as a low waste amount confirmed by the E-factor calculation, are in favor of controlled costs. Plasticizing properties of synthesized GC were compared to the behaviors of a commercial plasticizer and natural dialkyl carbonates, for a colorless nail polish formulation. The resulting films subjected to mechanical and thermal stresses (DMA and Persoz pendulum) showed the high plasticizing effect of GC toward nitrocellulose based films, probably due to hydrogen bond interactions between GC and nitrocellulose. The GC efficiency gives the possibility to decrease the content of the plasticizer in the formulation. Glycerol carbonate can be thus considered as a biobased ingredient abiding by the green chemistry concepts, and safe enough to be used in an ecodesigned nail polish formulation.

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Section: Research Update On Gc Synthesismentioning

confidence: 99%

“…- Homogeneous ammonium catalysts: tetraethylammonium pipecolinate gives the best results in terms of glycerol conversion and reaction selectivity (Van Mileghem et al, 2018).…”

Section: Research Update On Gc Synthesismentioning

confidence: 99%

See 1 more Smart Citation

Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Bandres

Urrutigoı̈ty

et al. 2019

Front. Chem.

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“…DMC has attracted attention as a less-toxic carbonyl source [42][43][44]. However, there are only a limited number of reports on the carbonation of glycerol with DMC under continuous-flow conditions using homogeneous catalysts [45,46]. The authors screened reaction parameters including residence time, temperature, glycerol/DMC molar ratios, and the amounts of catalysts.…”

Section: Solvent-free Organocatalytic Synthesis Of Cyclic Carbonatesmentioning

confidence: 99%

Recent Advances in Continuous-Flow Reactions Using Metal-Free Homogeneous Catalysts

2020

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Developments that result in high-yielding, low-cost, safe, scalable, and less-wasteful processes are the most important goals in synthetic organic chemistry. Continuous-flow reactions have garnered much attention due to many advantages over conventional batch reactions that include precise control of short reaction times and temperatures, low risk in handling dangerous compounds, and ease in scaling up synthesis. Combinations of continuous-flow reactions with homogeneous, metal-free catalysts further enhances advantages that include low-cost and ready availability, low toxicity, higher stability in air and water, and increased synthetic efficiency due to the avoidance of the time-consuming removal of toxic metal traces. This review summarizes recently reported continuous-flow reactions using metal-free homogeneous catalysts and classifies them either as acidic catalysts, basic catalysts, or miscellaneous catalysts. In addition, we compare the results between continuous-flow conditions and conventional batch conditions to reveal the advantages of using flow reactions with metal-free homogeneous catalysts.

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“…Baxendale and co‐workers explored a basic heterogeneous catalyst to promote the same reaction – Ambersep® 900 hydroxide resin. Different scale‐up procedures were tested, showcasing the robustness of this flow procedure, achieving high conversion rates and selectivities, allowing the production of glycerol carbonate at levels as high as 5.6 kg L –1 h –1 …”

Section: Heterocyclic Synthesismentioning

confidence: 99%

Flow Chemistry: Towards A More Sustainable Heterocyclic Synthesis

2019

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Flow Chemistry is a revolutionary field in Organic Chemistry. By changing the conventional methods and apparatus applied in the chemical synthesis, flow chemistry emerges as a game changer for organic synthesis laboratories, in both academia and industries. Considered as a sustainable practice, flow processes play an important role in the development of fine chemical products and in drug discovery development pro- [a] The main advantages of flow chemistry are that it allows the reaction to be carried out safely with high selectivity, high reproducibility and reduced energy consumption/carbon footprint. These features make this emerging technology for organic synthesis desirable for green and sustainable chemical synthesis, giving the chemist time for work planning and design, instead of using it in repetitive tasks, [5b,12] as expressed by the CHEM21 project by awarding a green flag for continuousflow reactions, in opposition to an amber flag for those performed under batch conditions. [13] Pedro Brandão received his MSc in Pharmaceutical Sciences from the Faculty of Pharmacy -University of Porto, in 2011. Pursuing his passion on studies in the field of Drug Discovery and Development, he is currently undergoing his PhD studies in Chemistry, in the field of Catalysis and Sustainability. His main focus of work is the discovery of new drug candidates through sustainable techniques. Marta Pineiro received her Ph.D. in Organic Chemistry in 2003 in the University of Coimbra, Portugal, and since 2002 has been enrolled at the University of Coimbra, being at present Auxiliary Professor. Her research interests are in the area of sustainable organic synthesis, microwave-assisted organic synthesis and synthesis and biological applications of tetrapyrrolic macrocycles. Teresa M. V. D. Pinho e Melo studied Chemistry at the University of Coimbra, where she graduated in 1985, got her M. 7191CPBA) as the oxidizing agent, avoiding the handling of this expensive and explosive reagent. [25] Recently, Morodo et al. explored the synthesis of two very important oxiranes (epichlorohydrin and glycidol) from biobased glycerol, under flow conditions. As depicted in Scheme 1, and using pimelic acid as the catalyst (10 mol-%), a sequential hydrochlorination/dichlorination process allows high conversion of glycerol (> 99 %) into 1,3-dichloro-2-propanol, followed by the quantitative conversion into a separable mixture of glycidol and epichlorohydrin (2:3). The separation of these two products is performed by an in-line membrane separation system, which allows the first product to be collected in the aqueous phase, while the second is collected in MTBE. This heterocycle can be further used as a synthetic precursor to relevant APIs bearing -amino alcohol moieties (e.g., propranolol, alprenolol and naftopidil). [26] Scheme 1. Sequential flow setup for the preparation of glycidol and epichlorohydrin, important APIs synthetic intermediates.Scheme 3. Synthesis and inline purification of a bicyclic aziridine (SGMR = silicon-glass microfluidic react...

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A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

Cited by 19 publications

References 60 publications

Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Recent Advances in Continuous-Flow Reactions Using Metal-Free Homogeneous Catalysts

Flow Chemistry: Towards A More Sustainable Heterocyclic Synthesis

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