Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents

2014 ◽  
Vol 50 (68) ◽  
pp. 9650-9652 ◽  
Author(s):  
James Sherwood ◽  
Mario De bruyn ◽  
Andri Constantinou ◽  
Laurianne Moity ◽  
C. Rob McElroy ◽  
...  
Keyword(s):  
Aprotic Solvent ◽  
Aprotic Solvents ◽  
Dipolar Aprotic Solvent ◽  
Dipolar Aprotic Solvents

Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent.

Solvation of Ions. V. Rates of SN2 Reactions in Mixtures of Protic and Dipolar Aprotic Solvents

1963 ◽  
Vol 16 (4) ◽  
pp. 585 ◽  
Author(s):  
AJ Parker
Keyword(s):  
Aprotic Solvent ◽  
Chloride Ion ◽  
Solvent Mixtures ◽  
Protic Solvent ◽  
Dipolar Aprotic Solvent ◽  
Sn2 Reactions ◽  
Protic Solvents ◽  
Bonding Interaction ◽  
Solvation Of Ions ◽  
Dipolar Aprotic Solvents

The rates of reaction of methyl iodide with chloride ion in some protic-dipolar aprotic solvent mixtures have been measured. The rate-retarding effect of protic solvents at M concentration in dimethylacetamide is in the order p-NO2C6H4OH > C6H5OH > C6H5SH > C6H5CO2H ≈ CH3OH > C6H5NH2 >H2O ≈ D2O. Protic solvents slow the reaction by a general rather than a specific hydrogen bonding interaction with the anion. Both the dipolar aprotic solvent and the protic solvent, as well as the anion, accept hydrogen bonds, and this influences the interaction between protic solvent and anion.

scholarly journals Basicité de solvants dipolaries aprotoniques

1976 ◽  
Vol 54 (13) ◽  
pp. 2101-2109 ◽  
Author(s):  
Robert Domain ◽  
Marcel Rinfret ◽  
Robert L. Benoit
Keyword(s):  
Gas Phase ◽  
Aprotic Solvent ◽  
Aprotic Solvents ◽  
Fluorosulfonic Acid ◽  
Calorimetric Data ◽  
Proton Affinities ◽  
Enthalpy Changes ◽  
Solvent Basicity ◽  
Enthalpy Of Protonation ◽  
Dipolar Aprotic Solvents

The basicities of five dipolar aprotic solvents, sulfolane, propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and of water have been characterized by using as parameter the solvation enthalpy of the gaseous proton. The corresponding values of ΔH(g → s)(H+) are deduced from experimental calorimetric data on the reaction HCl(g) → H+(s) + Cl−(s) and the known enthalpy changes for H+(g) → H+(aq) and Cl−(aq) → Cl−(s). The transfer enthalpies of Cl− from water to solvent are estimated on the basis of an extrathermodynamic assumption. The values obtained for ΔH(g → s)(H+) are (kcal mol−1): TMS(−252.6), AN(−256.6), PC(−259.5), H2O(−270.0), DMF(−276.7), DMSO(−276.1). These values are compared to other parameters currently used to define the basicity of these solvents whether as molecules or as media. Thus, proton affinities are such that in the gas phase, acetonitrile is more basic than water by 17 kcal mol−1, while in the liquid phase our results indicate that acetonitrile is less basic than water by 13 kcal mol−1. This variation of 30 kcal mol−1 is attributed to differences in the nature of the solvated proton H+(s) in both solvents: several indications suggest that H+(s) is present as H+(AN)2 in AN, an aprotic solvent, while it is stabilized as H+(H2O)n in water, a protic solvent because of the formation of hydrogen bonds of a cooperative nature. Solvent basicity orders as defined with respect to ΔH(g → s)(H+) and ΔH(g → s)(HA) are shown to differ and the consequences as to the solvent effect on the dissociation of acids HA are considered. Further, there is a nearly linear relationship for the five dipolar aprotic solvents between the values of ΔH(g → s)(H+) and the enthalpy of protonation in fluorosulfonic acid.

Solvation of ions by dipolar aprotic solvents and water. A CNDO/2 study

1985 ◽  
Vol 50 (11) ◽  
pp. 2493-2508 ◽  
Author(s):  
Petr Kyselka ◽  
Zdeněk Havlas ◽  
Ivo Sláma
Keyword(s):  
Binary Mixtures ◽  
Quantum Chemical ◽  
Chemical Method ◽  
Molecular Structures ◽  
Dimethyl Sulphoxide ◽  
Ternary Mixtures ◽  
Aprotic Solvents ◽  
Quantum Chemical Method ◽  
Solvation Of Ions ◽  
Dipolar Aprotic Solvents

Solvation of Li+, Be2+, Na+, Mg2+, and Al3+ ions has been studied in binary mixtures with dimethyl sulphoxide, dimethylformamide, acetonitrile and water, and in ternary mixtures of the organic solvents with water. The CNDO/2 quantum chemical method was used to calculate the energies of solvation, molecular structures and charge distributions for the complexes acetonitrile...ion (1:1, 2:1, 4:1), dimethyl sulphoxide...ion (1:1), dimethylformamide...ion (1:1), and acetonitrile (dimethyl sulphoxide, dimethylformamide)...ion...water (1:1:1).

1H and 13C NMR spectra of 2,2’-disubstitutedtrans-azobenzenes suitable for preparation of metallized azo dyes

1991 ◽  
Vol 56 (10) ◽  
pp. 2160-2168 ◽  
Author(s):  
Josef Jirman
Keyword(s):  
Nmr Spectra ◽  
Electron Pair ◽  
Phenyl Group ◽  
Aprotic Solvents ◽  
1H And 13C Nmr ◽  
Predominant Form ◽  
Rapid Equilibrium ◽  
Dipolar Aprotic Solvents ◽  
Free Electron Pair ◽  
C Nmr

The 1H and 13C NMR spectra have been measured of six trans-azobenzenes substituted at 2 and 2’ positions with substituents favourable for complex formation with a metal (OH, NH2, NHCOCH3, COOH). From the standpoint of NMR such substituted trans-azobenzenes are present in solution in a rapid equilibrium following from rotation around the bond between C-1 of phenyl group and N atom of azo linkage. The predominant form has the substituent in the syn-position with respect to the free electron pair of the nearer azo nitrogen atom. The equilibrium is affected by dipolar aprotic solvents (such as hexadeuteriodimethyl sulfoxide) by decreasing the presence of the predominant form by 1 to 11%.

scholarly journals Butadiene sulfone as ‘volatile’, recyclable dipolar, aprotic solvent for conducting substitution and cycloaddition reactions

2015 ◽  
Vol 3 (1) ◽  
Author(s):  
Yong Huang ◽  
Esteban E. Ureña-Benavides ◽  
Afrah J. Boigny ◽  
Zachary S. Campbell ◽  
Fiaz S. Mohammed ◽  
...  
Keyword(s):  
Aprotic Solvent ◽  
Cycloaddition Reactions ◽  
Dipolar Aprotic Solvent

scholarly journals The comparative study of linear solvatation energy relationship for the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents

2012 ◽  
Vol 77 (10) ◽  
pp. 1311-1338 ◽  
Author(s):  
Sasa Drmanic ◽  
Jasmina Nikolic ◽  
Aleksandar Marinkovic ◽  
Bratislav Jovanovic
Keyword(s):  
Solvent Effects ◽  
Kinetic Data ◽  
Aprotic Solvent ◽  
Isonicotinic Acid ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Reaction Rates ◽  
Aprotic Solvents ◽  
Pyridine Carboxylic ◽  
The Comparative Study

Protic and aprotic solvent effects on the reactivity of picolinic, nicotinic and isonicotinic acid, as well as of some substituted nicotinic acids with diazodiphenylmethane (DDM) were investigated. In order to explain the kinetic results through solvent effects, the second-order rate constants for the reaction of the examined acids with DDM were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of the multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of the contributions of the initial and the transition state. The signs of the equation coefficients support the already known reaction mechanism. The solvatation models for all the investigated acids are suggested and related to their specific structure.

Electron-transfer reactions in non-aqueous media. VII. Reduction of CoF(NH3)52+ and Co(HCOO)(NH3)52+ by copper(I) in dimethyl sulfoxide-water mixtures

1983 ◽  
Vol 36 (10) ◽  
pp. 1923 ◽  
Author(s):  
JMB Harrowfield ◽  
L Spiccia ◽  
DW Watts
Keyword(s):  
Electron Transfer ◽  
Dimethyl Sulfoxide ◽  
Aqueous Media ◽  
Mixed Solvents ◽  
Transfer Reactions ◽  
Aprotic Solvents ◽  
Aqueous Mixtures ◽  
Electron Transfer Reactions ◽  
Dipolar Aprotic Solvents ◽  
Sphere Mechanism

Previous work on the reduction of a series of cobalt(III) complexes by iron(II) in dipolar aprotic solvents and in aqueous mixtures has been extended to reduction by copper(I). The greater stability of copper(I) to disproportionation in these media has permitted the study of the reduction of CoF(NH3)52+ and Co(HCOO)(NH3)52+ in range of solvents over a number of temperatures with a precision not possible in previous studies in water. The results are consistent with an inner-sphere mechanism in which the copper(I) reductant is preferentially solvated by dimethyl sulfoxide to the exclusion of water in mixed solvents.

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