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Several γ-valerolactone (GVL) based solvents including methyl 4-methoxyvalerate (1a), ethyl 4-ethoxyvalerate (1b), tetramethylammonium 4-hydroxyvalerate (2a), tetrabutylammonium 4-hydroxyvalerate (2b), and cholinium 4-hydroxyvalerate (2c) were prepared and characterized.Graphical abstract
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... ionic liquids. 11 The activation energies for viscous flow of 2a-c were 50.78 kJ, 53.53 kJ, and 46.28 kJ, respectively. These values are higher than normal liquids and liquid salts with higher melting points. 12 The conductivity of 2a-c increased exponentially (with a corre- lation factor higher than 0.99) when the temperature was increased (Fig. 4) T / K Figure 2. Density of 2a (C), 2b (-), 2c (:). Table 1 Vapor pressure of 1a and 1b ...
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C17H17NO4, monoclinic, P121/nl (no. 14), a = 11.426(3) Å, b = 10.450(3) Å, c = 13.779(3) Å, β = 99.75(2)°, V= 1621.6 ų, Z = 4, Rgt(F) = 0.056, wRref(F²) = 0.086, T = 292 K. © 2014 Oldenbourg Wissenschaftsverlag GmbH, Rosenheimer Str. 145, 81671 München. All rights reserved.
C26H22N2O4, triclinic P1̅, a = 8.035(3) Å, b = 10.387(4) Å, c = 13.126(5) Å, α = 83.831(10)°, β = 78.214(10)°, γ = 81.470(10)°, Z = 2, V = 1101.78(19) ų, Rgt(F) = 0.0663, wRref(F²) = 0.1830, T = 296(2) K.
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Citations
... Reproduced by permission from Inorganic Chemistry. [82]. Considering these things, J.M. Guarinos et al. has devised a new method for the conversion of Levulinic acid to γ-valerolactone (GVL) by MOF-808. ...
... 253 As for other biomass-derived solvents, GVL is characterized by low volatility and toxicity, high chemical stability at different pH with very low formation of peroxides, as well as good biodegradability. 254 In light of these very appealing features, in the last few years it was used as a sustainable reaction medium for several transition metal-catalyzed reactions, 255 including direct C-H bond arylation of (hetero) arenes. ...
Direct C-H bond arylation of (hetero)arenes is a very convenient approach for the synthesis of a wide variety of molecular targets, including compounds of pharmaceutical interest and π-conjugated small molecules and polymers. Compared to traditional transition metal-promoted cross-coupling reactions, direct C-H arylations best fit the Green Chemistry criteria, particularly in minimization of waste, use of less hazardous chemicals, atom economy, reduction of unnecessary derivatization steps. Despite the advantages, these reactions still initially suffered from major limitations in terms of sustainable chemistry, i.e., toxic and expensive transition-metal catalysts, toxic and/or hazardous solvents, high temperatures and long reaction times. The increasing attention towards environmentally friendly reaction protocols has boosted studies directed towards the development of sustainable strategies for direct C-H bond arylation of (hetero)arenes. This review offers a critical overview of the research on this topic, focusing on three main aspects: (i) recoverable catalysts; (ii) sustainable solvents; (iii) non-conventional energy sources.
... 7,8 It was investigated as a fuel additive, 8,9 illuminating and lighter fluid, 10 and a building block, preceding other chemical platform molecules and solvent. 11 Additionally, it presents several physicochemical properties of interest for a green solvent: relative lower vapor pressure, water miscibility favoring biodegradation, stability in water and air under normal conditions, and low toxicity. 7,8,12 In general, experimental data for new biobased chemicals are still scarce in the literature but represent a field of growing interest for industrial and academic purposes. ...
... , ln ln 0 ij ij ij ii jj (11) in which a ij , b ij , c ij , and d ij are adjustable binary interaction parameters; α ij is the nonrandomness parameter; and T is the temperature in Kelvin. After parameter regression for each system, liquid−liquid flash calculations were performed in the simulation mode by means of the decanter block for all experimental overall mixture points to check convergence. ...
... 6,7 At present, there are many natural responses and changes like hydrogenation, steam transforming responses, reductive amination of alcohols, hydro-dechlorination, incomplete oxidation, and dry improvement of methane completed over a bolstered nickel catalyst. [8][9][10][11][12][13][14] Over every one of these responses, hydrogenation is the most utilized one in both modern and research facilities. Elastomers, semi-inflexible and polyurethane (PU) created from fundamental compounds like Methylene diphenyl diisocyanate (MDI) and it is delivered from Aniline (AN). ...
Activated carbon (RHAC) and Silica (RHSiO2) both were prepared from Rice Husk (RH) with very simple methods. These supports were used for the preparation of Ni catalyst for hydrogenation of nitrobenzene by wet impregnation and reductive deposition method. Ni/RHSiO2 and Ni/RHAC catalysts are characterized by BET, XRD, SEM, and TPR techniques. Well, dispersion of Ni on these supports shows excellent conversion of nitrobenzene to Aniline.
... [54] LA esters, e.g. the methyl, ethyl and n-butyl levulinate can be used as diesel additives. [55,56] LA or its esters can also be hydrogenated to γ-valerolactone (GVL) which has excellent properties as a solvent [57,58] and can be used as a raw material for nylon intermediates, [59][60][61][62] a fuel additive, [63,64] and for high value chemicals [65][66][67][68] (Scheme 10). GVL has a sweet, creamy and nutty taste and smell and is therefore applied in the flavor and fragrance industry. ...
A modern trend to carbon dioxide neutral production processes is based on renewable raw materials derived from sugars. Herein, an overview on modern approaches to fine chemicals for the nutritional industry is presented. In comparison to the traditional fossil-fuel-based processes the development of sustainable alternative transformations is necessary to enable the full potential of the new sustainable feedstocks.
... Numerous examples of bio-derived organic solvents that can replace traditional fossil-based organic solvents are known. Limonene (derived from citrus peel) has been shown to replace toluene in the cleaning sector [23] or to break azeotrope in the diisopropyl ether/acetone vaporliquid equilibrium [24]; other examples of bio-based solvents are γ-valerolactone [25], 2-methyltetrahydrofuran [26], and dihydrolevoglucosenone (Cyrene) [27,28], among others [3,22]. ...
The solid–liquid equilibrium (SLE) behavior and liquid–liquid extraction (LLX) abilities of deep eutectic solvents (DESs) containing (a) thymol and L-menthol, and (b) trioctylphosphine oxide (TOPO) and L-menthol were evaluated. The distribution coefficients (KD) were determined for the solutes relevant for two biorefinery cases, including formic acid, levulinic acid, furfural, acetic acid, propionic acid, butyric acid, and L-lactic acid. Overall, for both cases, an increasing KD was observed for both DESs for acids increasing in size and thus hydrophobicity. Furfural, being the most hydrophobic, was seen to extract the highest KD (for DES (a) 14.2 ± 2.2 and (b) 4.1 ± 0.3), and the KD of lactic acid was small, independent of the DESs (DES (a) 0.5 ± 0.07 and DES (b) 0.4 ± 0.05). The KD of the acids for the TOPO and L-menthol DES were in similar ranges as for traditional TOPO-containing composite solvents, while for the thymol/L-menthol DES, in the absence of the Lewis base functionality, a smaller KD was observed. The selectivity of formic acid and levulinic acid separation was different for the two DESs investigated because of the acid–base interaction of the phosphine group. The thymol and L-menthol DES was selective towards levulinic acid (Sij = 9.3 ± 0.10, and the TOPO and L-menthol DES was selective towards FA (Sij = 2.1 ± 0.28).
... GVL is a stable, colorless water-soluble liquid with a boiling point of 207-208 °C [68,69]. It does not decompose at room temperature and has melting point of −31 °C [70,71]. These properties make it a promising green solvent which can replace many conventional dipolar aprotic solvents in industry and academia. ...
Solvents are an inevitable part of industries. They are widely used in manufacturing and processing industries. Despite the numerous controlling measures taken, solvents contaminate our environment to a vast extent. Green and sustainable solvents have been a matter of growing interest within the research community over the past few years due to the increasing environmental concerns. Solvents are categorized as “green” based on their nonvolatility, nonflammability, availability, biodegradability and so on. The use of ionic liquids, super critical carbon dioxide and aqueous solvents for the fabrication of polymer composites is discussed in this review. The progress of utilizing solvent-free approaches for polymer composite preparation and efforts to produce new biobased solvents are also summarized.
... Most importantly, GVL has been identified as a petrol additive [27] that can potentially greatly reduce the emission of carbon monoxide [32], a sustainability issue faced by large cities around the globe. Additionally, it is also used as a green solvent, food additives, or perfume [33,34]. For instance, Al-Shaal et al. reported the solvent-free hydrogenation of GVL to 2-MTHF in the presence of a Ru/C catalyst, achieving an MTHF yield of 43%. ...
Catalytic hydrogenation of a biomass-derived molecule, levulinic acid (LA), to γ-valerolactone (GVL) has been getting much attention from researchers across the globe recently. This is because GVL has been identified as one of the potential molecules for replacing fossil fuels. For instance, GVL can be catalytically converted into liquid alkenes in the molecular weight range close to that found in transportation fuels via a process that does not require an external hydrogen source. Noble and non-noble metals have been used as catalysts for the selective hydrogenation of LA to GVL. Of these, Ru has been reported to be the most active metal for this reaction. The type of metal supports and solvents has been proved to affect the activity, selectivity, and yields of GVL. Water has been identified as a potential, effective “green” solvent for the hydrogenation of LA to GVL. The use of different sources of H2 other than molecular hydrogen (such as formic acid) has also been explored. In a few instances, the product, GVL, is hydrogenated further to other useful products such as 1,4-pentanediol (PD) and methyl tetrahydrofuran (MTHF). This review selectively focuses on the potential of immobilized Ru catalysts as a potential superior catalyst for selective hydrogenation of LA to GVL.
... Interestingly, it was found to be an excellent solvent for the biotransformation of biomasses into different chemicals [19]. It is also a source for numerous GVL-derived green solvents such as alkyl 4-alkoxyvalerate and GVL-derived ionic liquids (ILs) [20]. ...
This chapter presents the basics and applications of biosolvents as alternative eco-compatible and harmless media for biocatalyzed reactions. It begins with an introduction about the main sources of biosolvents and their production via the biorefinery concept. Then, a classification of the biosolvents according to their chemical structure is discussed with many examples. The various applications of biosolvents in different biocatalytic processes are expounded demonstrating the principle of the applications and the significant advantages of utilizing the biosolvents.
... Over the past 10 years several papers have reported the use of less hazardous solvents for SPPS which include the following greener solvents: water, cyclopentyl methyl ether (CPME), methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), acetonitrile (ACN), 2-methyltetrahydrofuran (Me-THF) (4,29), ethyl acetate (EtOAc) (4,30), dimethyl carbonate (DMC), γ-valerolactone (GVL) (31,32), N-formylmorpholine (33) and most recently the use of N-butylpyrrolidinone (NBP), which is characteristically similar to NMP but is not classified as either reprotoxic or mutagenic (34,35). The use of NBP has been reported by Novartis for the synthesis of octreotide, an eight amino acid peptide. ...
Polar aprotic solvents such as N,N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), N,N’-dimethylacetamide (DMAc) and chlorinated solvent such dichloromethane (DCM) are the most widely used solvents for Fmoc solid-phase peptide synthesis (SPPS). These solvents are considered hazardous chemicals but are normally used in large amounts for washing, deprotection, and coupling steps during SPPS. DMF, DMAc and NMP are classified as toxic for reproduction in accordance with Article 57(c) of REACH (Registration, Evaluation Authorization and Restriction of CHemicals) and were identified as SVHC (Substance Very High Concern). The aim of this study was to find a greener solvent alternative which could replace DMF in SPPS manufacturing processes at Ipsen. Greener solvents which demonstrated efficient resin swelling and solubility were selected as candidates for SPPS trials for the small-scale synthesis of commercial and developmental peptides.
