Diformylxylose as a new polar aprotic solvent produced from renewable biomass

Komarova, Anastasia O.; Luterbacher, Jeremy S.

doi:10.1039/d1gc00641j

Cited by 22 publications

(9 citation statements)

References 50 publications

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“…Solvation properties, including polarity, dispersion forces, and hydrogen-bonding strength, are important factors for controlling solubility, reaction rates, product isolation, etc Table shows a comparison of Kamlet–Abboud–Taft (KAT) parameters and Hansen solubility parameters (HSPs) of 1 compared to other solvents.…”

Section: Resultsmentioning

confidence: 99%

2,5-Diethyl-2,5-Dimethyloxolane (DEDMO) as a Nonpolar, Nonperoxide-Forming Ether Solvent for Organic Synthesis

Noppawan

Sangon

Supanchaiyamat

et al. 2022

ACS Sustainable Chem. Eng.

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The development of safer and more sustainable solvents is an important discipline in the context of stricter regulations and environmental protection. This work demonstrates the sustainable synthesis of a potentially bio-based, inherently nonperoxide-forming ether solvent, namely, 2,5-diethyl-2,5-dimethyloxolane (DEDMO), in quantitative yields with high atom economy (97%) and reaction mass efficiency (94%) from renewable sources. Quantum mechanical calculations of theoretical NMR chemical shifts and DP4+ probability modeling indicated that the cis isomer of DEDMO was most plausible (with a probability value of 99.98%); however, the actual NMR data suggested a 1:1 mixture of cis and trans isomers for DEDMO. The solvation properties of DEDMO have also been evaluated using Kamlet–Abboud–Taft (KAT) parameters, Hansen solubility parameters (HSPs), and in silico modeling COSMO-RS. The KAT parameter relating to a combined effect of solvent polarity and polarizability (π*) was 0.32 for DEDMO, which was lower than other quaternary ethers such as 2,2,5,5-tetramethyloxolane (TMO) (0.35) and cineole (0.41). In silico COSMO-RS modeling suggested that DEDMO has similar characteristics to hydrocarbon solvents such as n-hexane or toluene. The substitution of all hydrogen atoms at the α-position to the ethereal oxygen with an alkyl group, such as the methyl and ethyl groups of DEDMO, inhibits its ability to form explosive peroxides. Moreover, the steric concealment of the ethereal oxygen of DEDMO leads to similar properties to hydrocarbon solvents rather than traditional ether solvents. The performance of DEDMO as a solvent is demonstrated in an enzymatic esterification, as well as heterocyclic synthesis by means of a Biginelli reaction, and annulation reactions. Application testing of DEDMO revealed that its behavior was similar in solvent properties to hydrocarbon solvents; in fact, results were typically between those of toluene and n-hexane. The presence of ethyl groups enhances its nonpolar character, and as such, DEDMO was demonstrated to perform better than the green quaternary ethers TMO in some reactions. Preliminary in silico toxicity predictions indicate that DEDMO is nonmutagenic, and thus DEDMO is a potentially green hindered ether solvent for the substitution of conventional nonpolar solvents.

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Section: Resultsmentioning

confidence: 99%

2,5-Diethyl-2,5-Dimethyloxolane (DEDMO) as a Nonpolar, Nonperoxide-Forming Ether Solvent for Organic Synthesis

Noppawan

Sangon

Supanchaiyamat

et al. 2022

ACS Sustainable Chem. Eng.

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“…The experimentally reported activation barrier for Pyr+MeBr in methanol is 22.5 kcal/mol which is 3.1 and 5.1 kcal/mol lower, respectively, compared with apolar cyclohexane and di- n -butyl ether . Further, an almost linear relationship between the natural log of the rate constants and polarity/polarizability of the solvents for the alkylation (Menshutkin) reaction between 1-bromodecane and 1,2-dimethylimidazol was observed . DMSO was found to be the best solvent for accelerating the rate of heteroatom alkylations.…”

Section: Introductionmentioning

confidence: 88%

“…1 Further, an almost linear relationship between the natural log of the rate constants and polarity/polarizability of the solvents for the alkylation (Menshutkin) reaction between 1-bromodecane and 1,2-dimethylimidazol was observed. 58 DMSO was found to be the best solvent for accelerating the rate of heteroatom alkylations.…”

Section: Introductionmentioning

confidence: 92%

Solvent Effects on the Menshutkin Reaction

2022

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The Menshutkin reaction is a methyl transfer reaction relevant in fields ranging from biochemistry to chemical synthesis. In the present work, the energetics and solvent distributions for NH3+MeCl and Pyr+MeBr reactions were investigated in explicit solvent (water, methanol, acetonitrile, benzene, cyclohexane) by means of reactive molecular dynamics simulations. For polar solvents (water, methanol, and acetonitrile) and benzene, strong to moderate catalytic effects for both reactions were found, whereas apolar and bulky cyclohexane interacts weakly with the solute and does not show pronounced barrier reduction. The calculated barrier heights for the Pyr+MeBr reaction in acetonitrile and cyclohexane are 23.2 and 28.1 kcal/mol compared with experimentally measured barriers of 22.5 and 27.6 kcal/mol, respectively. The solvent distributions change considerably between reactant and TS but comparatively little between TS and product conformations of the solute. As the system approaches the transition state, correlated solvent motions occur which destabilize the solvent–solvent interactions. This is required for the system to surmount the barrier. Finally, it is found that the average solvent–solvent interaction energies in the reactant, TS, and product state geometries are correlated with changes in the solvent structure around the solute.

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“… 2 Recently, new candidates such as diformylxylose have also been proposed as a replacements for traditional dipolar aprotics, though no toxicity studies have yet been conducted on this solvent. 60 Also of significance is the growing body of literature employing these alternative reaction solvents and conditions. The growth of literature adopting greener, more sustainable solvents is reinforcing the position that these replacement solvents are genuinely an improvement on the current state of the art and are a credible alternative to the current status quo.…”

Section: Introductionmentioning

confidence: 99%

“…Instead, it is suggested that significantly important transformations employed in medicinal chemistry, such as amide bond formation and metal catalyzed cross-coupling, can be conducted in surfactant–water systems. ,− Key developments have also been made in identifying and discovering new dipolar aprotic solvents with improved safety, sustainability, and green chemistry criteria such as N -butyl-2-pyrrolidinone, propylene carbonate, dimethyl isosorbide, and dihydrolevoglucosenone (Cyrene) . Recently, new candidates such as diformylxylose have also been proposed as a replacements for traditional dipolar aprotics, though no toxicity studies have yet been conducted on this solvent . Also of significance is the growing body of literature employing these alternative reaction solvents and conditions.…”

Section: Introductionmentioning

confidence: 99%

Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives

et al. 2022

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Dipolar aprotic and ethereal solvents comprise just over 40% of all organic solvents utilized in synthetic organic, medicinal, and process chemistry. Unfortunately, many of the common “go-to” solvents are considered to be “less-preferable” for a number of environmental, health, and safety (EHS) reasons such as toxicity, mutagenicity, carcinogenicity, or for practical handling reasons such as flammability and volatility. Recent legislative changes have initiated the implementation of restrictions on the use of many of the commonly employed dipolar aprotic solvents such as dimethylformamide (DMF) and N -methyl-2-pyrrolidinone (NMP), and for ethers such as 1,4-dioxane. Thus, with growing legislative, EHS, and societal pressures, the need to identify and implement the use of alternative solvents that are greener, safer, and more sustainable has never been greater. Within this review, the ubiquitous nature of dipolar aprotic and ethereal solvents is discussed with respect to the physicochemical properties that have made them so appealing to synthetic chemists. An overview of the current legislative restrictions being imposed on the use of dipolar aprotic and ethereal solvents is discussed. A variety of alternative, safer, and more sustainable solvents that have garnered attention over the past decade are then examined, and case studies and examples where less-preferable solvents have been successfully replaced with a safer and more sustainable alternative are highlighted. Finally, a general overview and guidance for solvent selection and replacement are included in the Supporting Information of this review.

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Diformylxylose as a new polar aprotic solvent produced from renewable biomass

Abstract: Demand for sustainable polar aprotic solvents is increasing due to their unique solubilizing properties and the toxicity of conventional analogs, which are facing pressure from extensive safety legislation. Polar aprotic...

Cited by 22 publications

References 50 publications

2,5-Diethyl-2,5-Dimethyloxolane (DEDMO) as a Nonpolar, Nonperoxide-Forming Ether Solvent for Organic Synthesis

2,5-Diethyl-2,5-Dimethyloxolane (DEDMO) as a Nonpolar, Nonperoxide-Forming Ether Solvent for Organic Synthesis

Solvent Effects on the Menshutkin Reaction

Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives

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