Process intensification for tertiary amine catalyzed glycerol carbonate production: translating microwave irradiation to a continuous-flow process

Nogueira, Daniel O.; Souza, Stefânia P. de; Leão, Raquel A. C.; Miranda, Leandro S. M.; Souza, Rodrigo O. M. A. de

doi:10.1039/c5ra02117k

Cited by 29 publications

(16 citation statements)

References 65 publications

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“…The relative flow rate was adjusted in such a way as to provide 3.5 equivalents of DMC. Initially, we adopted the protocol from the de Souza group using neat glycerol with catalyst, preheated at 70 °C (Tab. , entry 1).…”

Section: Resultsmentioning

confidence: 99%

“…Many catalysts are known for this transesterification, e.g., inorganic bases [27][28][29][30], tertiary amines [31][32][33][34], lipases [35][36][37], and N-heterocyclic carbenes [38]. However, only a few continuous processes are known for this transformation [39][40][41][42] while, in general, continuous processes more often meet the basic criteria for potential industrial feasibility and scale-up. To the best of our knowledge, inorganic bases are the preferred catalysts of use for the industrial preparation of 2-GLC prepared from glycerol and DMC, mainly based upon cost [23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

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A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

2018

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With glycerol being a bulk waste product, the interest in converting it to other value‐added products is steadily increasing. A scalable continuous flow process was developed for the synthesis of glycerol carbonate (2‐GLC) from glycerol and dimethyl carbonate on a hydroxide functional resin. High conversion and selectivity were obtained while the residence times were typically shorter than 10 min. Continuous production of 2‐GLC was achieved in high throughput and with improved processing metrics, creating the foundations for a production level process.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

2018

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“…described a DBU‐catalyzed synthesis of this high‐value product at 120 °C, using glycerol and dimethyl carbonate as starting materials. The homogeneous catalytic flow setup proved to be suitable for process intensification, affording the product with yield up to 90 % (24 kg L –1 day –1 ) . Baxendale and co‐workers explored a basic heterogeneous catalyst to promote the same reaction – Ambersep® 900 hydroxide resin.…”

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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“…The interest in improving the process efficiency of biodiesel production is rising along with the reduced economic feasibility of glycerol due to overproduction . The transformation of glycerol into high value‐added chemicals is desirable including 1,3‐propanediol, propylene glycol, acrolein, epichlorohydrin, glycidol and glycerol carbonate (GC), the most important product reported in the last 5 years . Glycerol carbonate (GC) can be synthesized by different routes using glycerol as alcohol source and chemicals such as CO/O 2, organic carbonate, urea or carbon dioxide as carbonate source.…”

Section: Introductionmentioning

confidence: 99%

Immobilization of lipase B from Candida antarctica on epoxy‐functionalized silica: characterization and improving biocatalytic parameters

Souza

Almeida

Leão

et al. 2017

J of Chemical Tech & Biotech

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BACKGROUND: In this work, lipase B from Candida antarctica (CaLB) was immobilized on Purolite ® ECR8205F, Purolite ® ECR8214F and Immobead ® IB150 P epoxy resins with no modification to their surfaces. Biocatalysts were evaluated for thermal stability and applied in reactions of hydrolysis, esterification and the synthesis of glyceryl carbonate by transesterification with dimethyl-carbonate both with glycerol and Macauba oil as well as dynamic kinetic resolution of -methylbenzylamine, all of them compared with commercial Novozyme 435 ® .

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Process intensification for tertiary amine catalyzed glycerol carbonate production: translating microwave irradiation to a continuous-flow process

Abstract: Different products of interest can be produced from glycerol and glycerol carbonate (GC) has received much attention in recent years because of its physical properties, nontoxicity and water solubility.

Cited by 29 publications

References 65 publications

A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

A Robust and Scalable Continuous Flow Process for Glycerol Carbonate

Flow Chemistry: Towards A More Sustainable Heterocyclic Synthesis

Immobilization of lipase B from Candida antarctica on epoxy‐functionalized silica: characterization and improving biocatalytic parameters

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