scholarly journals Towards the development of continuous, organocatalytic, and stereoselective reactions in deep eutectic solvents

2016 ◽  
Vol 12 ◽  
pp. 2620-2626 ◽  
Author(s):  
Davide Brenna ◽  
Elisabetta Massolo ◽  
Alessandra Puglisi ◽  
Sergio Rossi ◽  
Giuseppe Celentano ◽  
...  
Keyword(s):  
Organic Solvent ◽  
Reaction Rate ◽  
Deep Eutectic Solvent ◽  
Deep Eutectic Solvents ◽  
High Yield ◽  
Aldol Reactions ◽  
Experimental Conditions ◽  
Stereoselective Reactions ◽  
Reaction Media ◽  
Very High

Different deep eutectic solvent (DES) mixtures were studied as reaction media for the continuous synthesis of enantiomerically enriched products by testing different experimental set-ups. L-Proline-catalysed cross-aldol reactions were efficiently performed in continuo, with high yield (99%), anti-stereoselectivity, and enantioselectivity (up to 97% ee). Moreover, using two different DES mixtures, the diastereoselectivity of the process could be tuned, thereby leading to the formation, under different experimental conditions, to both the syn- and the anti-isomer with very high enantioselectivity. The excess of cyclohexanone was recovered and reused, and the reaction could be run and the product isolated without the use of any organic solvent by a proper choice of DES components. The dramatic influence of the reaction media on the reaction rate and stereoselectivity of the process suggests that the intimate architecture of DESs deeply influences the reactivity of different species involved in the catalytic cycle.

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2021 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology and materials science. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as green and “active” reaction media, has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these innovative solvents has shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be “active” in these transformations for the absence of added bases in all the performed reactions and in several cases, for their reducing capabilities. The reactions outcomes were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering of reagents and the possibility of recycling of the green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis. </p>

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2021 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology and materials science. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as green and “active” reaction media, has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these innovative solvents has shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be “active” in these transformations for the absence of added bases in all the performed reactions and in several cases, for their reducing capabilities. The reactions outcomes were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering of reagents and the possibility of recycling of the green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis. </p>

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2021 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology and materials science. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as green and “active” reaction media, has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these innovative solvents has shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be “active” in these transformations for the absence of added bases in all the performed reactions and in several cases, for their reducing capabilities. The reactions outcomes were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering of reagents and the possibility of recycling of the green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis. </p>

scholarly journals Pyrrolidinium salt based binary and ternary deep eutectic solvents: green preparations and physiochemical property characterizations

2018 ◽  
Vol 7 (4) ◽  
pp. 353-359 ◽  
Author(s):  
Jing Wang ◽  
Sheila N. Baker
Keyword(s):  
Melting Point ◽  
Large Scale ◽  
Deep Eutectic Solvent ◽  
Deep Eutectic Solvents ◽  
Industrial Applications ◽  
Economic Feasibility ◽  
Preparation Process ◽  
Green Solvents ◽  
Liquid Form ◽  
Reaction Media

Abstract Ionic liquids (ILs) are considered to be green solvents for various applications. However, their synthesis via chemical reaction with by-products or waste produced is contradictory to the concept of green chemistry, and the purity problem and economic feasibility limit their applications in some large-scale industrial applications. 1-Butyl-1-methylpyrrolidinium bromide ([bmpy][Br]), which is a molten salt with melting point above 100°C is a precursor of pyrrolidinium ILs, but hardly can be put under the category of IL because of its high melting point. In this study, [bmpy][Br] based binary deep eutectic solvent (BDES) and ternary deep eutectic solvent (TDES) were synthesized to prepare [bmpy][Br] in liquid form. During the preparation process, no reaction media was employed, no by-product was generated, and no further purification was required, thereby making it a completely green process. The prepared TDES has better thermal stability and larger free volume than BDES, which is potentially useful for sorption applications with high temperature requirement. It is also because of the green preparation process that the TDES is also expected to be capable for the large-scale industrial applications. This work is opening up new avenues for the study of binary and ternary IL-DES system and their applications.

scholarly journals Effective Extraction of Limonene and Hibaene from Hinoki (Chamaecyparis obtusa) Using Ionic Liquid and Deep Eutectic Solvent

Molecules ◽  
2021 ◽  
Vol 26 (14) ◽  
pp. 4271
Author(s):  
Rina Yasutomi ◽  
Riki Anzawa ◽  
Masamitsu Urakawa ◽  
Toyonobu Usuki
Keyword(s):  
Ionic Liquid ◽  
Organic Solvent ◽  
Essential Oils ◽  
Control Method ◽  
Deep Eutectic Solvent ◽  
Deep Eutectic Solvents ◽  
Chamaecyparis Obtusa ◽  
Molar Ratio ◽  
Gas Chromatography Mass Spectrometry ◽  
Selected Ion Monitoring

The essential oils of hinoki (Chamaecyparis obtusa) leaves have anti-bacterial, anti-fungal, and relaxation properties that are likely associated with the major components such as sabinene, α-terpinyl acetate, limonene, elemol, myrcene, and hibaene. The present study describes the use of a cellulose-dissolving ionic liquid (IL) [C2mim][(MeO)(H)PO2] and low-toxicity solvents called betaine-based deep eutectic solvents (DESs) for the efficient extraction of hinoki essential oils. As a control method, organic solvent extraction was performed using either hexane, ethyl acetate (EtOAc), or acetone at 30 °C for 1 h. Both the experimental and control methods were conducted under the same conditions, which relied on partial dissolution of the leaves using the IL and DESs before partitioning the hinoki oils into the organic solvent for analysis. Quantitative analysis was performed using gas chromatography–mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The results indicated that extraction using the [C2mim][(MeO)(H)PO2]/acetone bilayer system improved the yields of limonene and hibaene, 1.5- and 1.9-fold, respectively, when compared with the control method. In addition, extraction using betaine/l-lactic acid (molar ratio 1:1) gave the greatest yields for both limonene and hibaene, 1.3-fold and 1.5-fold greater, respectively, than when using an organic solvent. These results demonstrate the effective extraction of essential oils from plant leaves under conditions milder than those needed for the conventional method. The less toxic and environmentally begin DESs for the extraction are also applicable to the food and cosmetic industries.

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2020 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Chemical Biology ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<div><div><div><p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a transformation widely used to obtain relevant products in chemical biology, medicinal chemistry, materials science and other fields. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as “active” reaction media has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these green liquids as green and catalytic solvents has shown to improve the reaction effectiveness, giving excellent yields. The NADESs proved to be “active” in this transformation for the absence of added bases in all the performed reactions and in several cases for their reducing capabilities. The results were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering</p></div></div></div><div><div><div><p>of reagents and the possibility of recycling of these green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis.</p></div></div></div>

scholarly journals Enzymatic Synthesis of Glucose Monodecanoate in a Hydrophobic Deep Eutectic Solvent

2020 ◽  
Vol 21 (12) ◽  
pp. 4342 ◽  
Author(s):  
Rebecca Hollenbach ◽  
Katrin Ochsenreither ◽  
Christoph Syldatk
Keyword(s):  
Deep Eutectic Solvent ◽  
Deep Eutectic Solvents ◽  
Decanoic Acid ◽  
Significant Loss ◽  
Esterification Reaction ◽  
Initial Reaction ◽  
Reaction Velocity ◽  
Glycolipid Synthesis ◽  
Reaction Media ◽  
First Time

Environmentally friendly and biodegradable reaction media are an important part of a sustainable glycolipid production in the transition to green chemistry. Deep eutectic solvents (DESs) are an ecofriendly alternative to organic solvents. So far, only hydrophilic DESs were considered for enzymatic glycolipid synthesis. In this study, a hydrophobic DES consisting of (-)-menthol and decanoic acid is presented for the first time as an alternative to hydrophilic DES. The yields in the newly introduced hydrophobic DES are significantly higher than in hydrophilic DESs. Different reaction parameters were investigated to optimize the synthesis further. Twenty milligrams per milliliter iCalB and 0.5 M glucose resulted in the highest initial reaction velocity for the esterification reaction, while the highest initial reaction velocity was achieved with 1.5 M glucose in the transesterification reaction. The enzyme was proven to be reusable for at least five cycles without significant loss of activity.

Synthesis of β-sialon from coals or natural graphite

1995 ◽  
Vol 10 (3) ◽  
pp. 727-735 ◽  
Author(s):  
F.J. Narciso ◽  
A. Linares-Solano ◽  
F. Rodriguez-Reinoso
Keyword(s):  
Reaction Rate ◽  
Lower Proportion ◽  
The Other ◽  
High Yield ◽  
Mineral Matter ◽  
Nitrogen Flow ◽  
Natural Graphite ◽  
Intimate Contact ◽  
Additional Advantage ◽  
Very High

The synthesis of β-sialon has been carried out by heat treatment in nitrogen flow of Spanish coals or mineral graphite, both with a high content of mineral matter. The results were compared with those obtained with conventional clay/carbon mixtures. The coals and, especially, the mineral graphite produced a very high yield of β-sialon, with a faster reaction rate than the clay/carbon mixtures due to the more intimate contact among the reactants, with the additional advantage of forming much a lower proportion of vitreous phases. On the other hand, the results show that in the particular case of graphite, the use of high temperatures (even above 1450 °C) does not lead to changes in the crystalline phases of the product, allowing the synthesis to be carried out over a wider temperature range than that used for clay/carbon mixtures. The mechanical properties of the sintered artifacts obtained with the sialon synthesized from natural graphite are superior to those prepared from clay/carbon mixtures and comparable (or even superior) to commercial artifacts manufactured from much more expensive precursors.

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2020 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Chemical Biology ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<div><div><div><p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a transformation widely used to obtain relevant products in chemical biology, medicinal chemistry, materials science and other fields. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as “active” reaction media has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these green liquids as green and catalytic solvents has shown to improve the reaction effectiveness, giving excellent yields. The NADESs proved to be “active” in this transformation for the absence of added bases in all the performed reactions and in several cases for their reducing capabilities. The results were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering</p></div></div></div><div><div><div><p>of reagents and the possibility of recycling of these green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis.</p></div></div></div>

scholarly journals Investigation of Base-free Copper-Catalysed Azide–Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media

2021 ◽  
Author(s):  
Salvatore V. Giofrè ◽  
Matteo Tiecco ◽  
Angelo Ferlazzo ◽  
Roberto Romeo ◽  
Gianluca Ciancaleoni ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Materials Science ◽  
Cycloaddition Reaction ◽  
Deep Eutectic Solvents ◽  
Green Solvents ◽  
Experimental Conditions ◽  
Active Reaction ◽  
Natural Deep Eutectic Solvents ◽  
Catalytic Intermediates ◽  
Reaction Media

<p>The click cycloaddition reaction of azides and alkynes affording 1,2,3-triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology and materials science. In this work, a set of Natural Deep Eutectic Solvents (NADESs) as green and “active” reaction media, has been investigated in the copper-catalysed azide–alkyne cycloaddition reactions (CuAAc). The use of these innovative solvents has shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be “active” in these transformations for the absence of added bases in all the performed reactions and in several cases, for their reducing capabilities. The reactions outcomes were rationalized by DFT calculations which demonstrated the involvement of H-bonds between DESs and alkynes as well as a stabilization of copper catalytic intermediates. The green experimental conditions, namely the absence of a base, the low temperatures, the lowering of reagents and the possibility of recycling of the green solvents, outline the great potential of NADESs for CuAAc and in general, for green organic synthesis. </p>

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