Compensation Between the Entropic and Enthalpic Changes Arising from Changes in Solvent–Solvent Interactions in Mixed Solvents

A theorem presented by Professor Ben-Naim (J Phys Chem 82:874–885, 1978) states that the standard state enthalpy and entropy changes arising from changes in the solvent structure that are induced by solvation of a solute cancel exactly in the standard state Gibbs energy. In this paper this is explored by consideration of the thermodynamics of transfer of electrolytes in mixed solvents, using previously developed models of the solvation process. Two cases are considered. One is random solvation, where curvatures in plots of the transfer enthalpies and entropies, which arise from changes in solvent–solvent interactions, exactly compensate in the transfer Gibbs (free) energies, which are sensibly linear with solvent composition. The second type of system are those with strong preferential solvation where it is found that the transfer Gibbs energies can be accounted for quantitatively in terms of changes in the solute–solvent interactions, with no contribution from changes in solvent–solvent interactions. The results are entirely consistent with the Ben-Naim theorem.     

Microwave-prompted Rapid and Efficient Synthesis of Diacyl Thiosemicarbazides and Semicarbazides in Solvent and Catalyst Free Condition

Eighteen 1-aroyl-4-（2-iodobenzoyl）thiosemicarbazides and corresponding semicarbazides were synthesized in excellent yield under microwave irradiation in solvent and catalyst free condition.     

A Facile and Efficient Synthesis of Arylsulfonates and Arylsulfonyl Hydrazides under Solvent Free Conditions

Organosulfur compounds are useful materials and most of them have pharmacological properties. The sulfonic esters are important intermediates in organic synthesis and used as acaricides and thermal recording materials. The sulfonyl hydrazides are valuable as inhibitors, agrochemical fungicides, insecticides and photographic images. Some methods have been reported for preparing these compounds to date. Usually, these reactions were carried out in organic solvent[1,2]such as pyridine and DMF. Even up-to date solid-phase synthesis requires solvent. What's more, they have other drawbacks including long reaction time, producing much wastes and by-products, tedious experimental procedure.     

Molecular dynamics and the structure of macrocycles —Solvent acetonitrile interactions

Microwave complex permittivities,* = -J, are reported in the 1–90 GHz frequency range for the macrocycles 18-crown-6 (18C6) and 15C5 added to acetonitrile in stoichiometric proportions, in the solvent CCl₄ at 25°C. Digitized infrared spectra of the CN stretch ₂ vibration of acetonitrile for the same systems are reported in the 2300–2200 cm^–1 spectral region. The macrocycle 12C4 added to CH₃CN has also been investigated in the infrared. Both the dielectric relaxation and infrared results are interpreted in terms of macrocycle-acetonitrile interactions, probably involving a methyl-hydrogen to ethereal-oxygen interaction. These interactions with CH₃CN diminish in strength according to the sequence: 18C6 > 15C5 > 12C4.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Measurement and Correlation of the Ionic Conductivity of Ionic Liauid-Molecular Solvent Solutions

The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate （[Bmim][BF4]） or 1-n-butyl-3-methylimidazolium hexafluorophosphate （[Bmim][PF6]） and different molecular solvents （MSs） were measured at 298.15 K. The molar conductivity of the ionic liquids （ILs） increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.     

Thermodynamics of Solvent Extraction of Rare and Scattered Metal-Indium with Diethylhexylmonothiophosphoric Acid

IntroductionIndium has been widely used in electronic indus-try,butin nature itcoexists with other metals instead ofexisting as a single mine.Among all the methods avail-able,extraction is the most effective one for abstractingindium.However,it is challen…     

Solvent Effects on Two-Photon Absorption of Alkyne and Alkene π-bridging Chromophores

The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption (TPA) processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.     

Mild and Efficient Solvent‐Free Friedel–Crafts Acylation of Reserpine

The first mild, efficient, solvent‐free Friedel–Crafts acylation of reserpine has been developed, which resulted in the synthesis of 10‐ and 12‐acylated homologues in high overall yields.     

Solvent and Structural Effects on the Photoreduction of Cobalt(III)-Aryl Amine Complexes in Water–Organic Solvent Media*

Photoreduction of [Co(En)₂Cl(RC₆H₄NH₂)]²⁺ ions (where R = p-OMe, p-OEt, p-Me, m-Me, H, p-F, and m-OMe) in varying compositions of water–methanol and water–1,4-dioxane mixtures containing 15–40% (vol.) of organic co-solvent is carried out. Ultraviolet excitation of the above complexes in air-equilibrated solutions causes bleaching of its intense LMCT excited states with concurrent production of Co²⁺ion. As seen from the quantum yield data, _Co(II) increases smoothly with increasing content of organic co-solvent in the binary mixtures. The observed values indicate that the metal center is reduced by both ligands and solvent. The quantum yield _Co(II) is considerably affected by the substituent R of the amine, RC₆H₄NH₂ ligand. The effects of solvent and substituted ligands on the _Co(II) are estimated quantitatively using linear regression and multiple correlation methods. The former analysis was carried out using Grunwald–Winstein (Y) Gutmann donor number (DN ^N) and Krygowski–Fawcett E ^N _T (solvent empirical parameters). In addition, Kamlet–Taft's , , and * solvatochromic parameters were also used to study the effect of solute–solvent interaction. The effect of substitution on the aromatic amine ligand affects the quantum yield values, which was established using Hammett's substituent constant . Extensive tabulations of percentage contributions of these parameters, calculated using methods reported earlier, provide suitable values which are presumed to explain the quantitative effects of solvent and structural changes in the aromatic ligand on photoreduction of the cobalt(III) complexes.     

Solvent effects on the steady state photophysics of estrone and 17β-estradiol

Absorption and emission yields for estrone and 17β-estradiol were measured in a variety of room temperature solvents. Molar extinction coefficients were found to not vary as a function of solvent, while fluorescence yields were found to be significantly affected by the polarity and hydrogen-bond accepting ability of the solvent, with the yield for 17β-estradiol being highest in nonpolar, hydrogen-bond donating solvents, and lowest in the nonpolar, hydrogen-bond accepting solvent ethyl acetate. Estrone's emission yield was found to be a factor of ten smaller than 17β-estradiol's. Strong solvent and excitation wavelength dependences were found for the relative amounts of emission between estrone's two emission bands, with increased relative emission occurring in nonpolar aprotic solvents, and under higher excitation energies. These results are interpreted with the aid of vertical excitation energies from time-dependent density functional calculations using both explicit and implicit solvation models.     

Solvent‐Free Claisen Condensation of Isophorone and Verbenone with para‐Hydroxyethylaminobenzaldehydes

A solvent‐free Claisen condensation between isophorone or verbenone on two para‐hydroxyethylaminobenzaldehydes is described. The method provides the condensation products quickly and, in most cases, without chromatography.     

Solvent and additive-free selective aerobic allylic hydroxylation of β-pinene catalyzed by metalloporphyrins

Metallodeuteroporphyrins(MDPs) were employed as the catalysts for aerobic oxidation of β-pinene in absence of solvents and additives. Allylic hydroxylation products were found to be the main products from this protocol. The catalytic activity of MDPs with different metal nuclei and the influences of technological conditions on this reaction were investigated. This catalytic system has bright application prospect since only eco-friendly and readily available dioxygen were needed.     

Solvent‐Free Rapid Deprotection of Ketone and Aldehyde Oximes using Periodic Acid

Abstract

Ketone and aldehyde oximes can be readily converted to the corresponding carbonyl compounds in high yields under solvent‐free conditions when treated with periodic acid. Oximes bearing aliphatic C?C bonds can be selectively deoximated. The advantages of this protocol include a rapid reaction rate and a simple workup procedure. No volatile organic solvents are required in the reaction processes.     

Chemoselective and Solvent‐Free Thioacetalization of Aldehydes by a Catalytic Amount of NBS

A chemoselective, straightforward, and rapid method for thioacetalization of aldehydes by use of 1,2‐ethandithiol and a catalytic amount of N‐bromosuccinimide under solvent‐free conditions is reported. The reaction takes place in excellent yields and short reaction times.     

Hydrophobic Silica Sol Coatings on Textiles—the Influence of Solvent and Sol Concentration

Hydrophobic silica sol coatings on textiles were investigated with respect to the influence of the solvents and the concentration of the sol. For this purpose, two silica sols, prepared with the hydrophobic additives octyltriethoxysilane and perfluoroctyltriethoxysilane were diluted by different solvents: water, ethanol and aceton.In case of using pure water for dilution, the hydrophobicity of coated textiles decreases drastically with increasing dilution of the applied sol. For coatings on polyester fabrics or mixed fabrics made from polyester and cotton, the use of the organic solvents ethanol or aceton leads to significant hydrophobicity even in case of strong dilution down to a sol concentration < 1%. The hydrophobic effect of coated polyamide textile is less. The reason for different hydrophobicity of coated textiles resulting from the use of water instead of organic solvents is explained by different surface morphologies of the coatings deposited on the textile fibres, as observed by REM. In case of using organic solvents the coatings contain a more flat morphology which covers the fibres completely. In contrast, sols with higher water content lead to less adhesive coatings with crack formation.The use of a combination of water with less inflammable organic solvents such as di(propylene glycol) n-propyl ether (Dowanol^TM DPnP) in hydrophobic silica sols yields textile coatings with good hydrophobicity, even in case of low sol concentration. For practical application of textile coatings, especially silica sols with high water content are of interest, due to less risk of inflammation and lower ecological impact. Therefore, the use of water diluted hydrophobic silica sols with small amounts of DPnP offers a chance for textile refinement by the sol–gel technique.     

Uncatalyzed and Solvent‐Free Process for the Synthesis of 1,4‐Diarylquinoline Derivatives

The uncatalyzed and three‐component reaction of arylaldehyde, malonodinitrile, and 3‐arylamino‐5,5‐dimethylcyclohex‐2‐enone at 160 °C under solvent‐free conditions gave 1,4‐diarylquinoline derivatives in high yields.     

Convenient and Regioselective One‐Pot Solvent‐Free Synthesis of ß‐Hydroxyphosphonates

A simple, efficient, regioselective, and solvent‐free method has been developed for the synthesis of β‐hydroxyphosphonates from epoxides and triethyl phosphite using ZnCl₂ in high yields under mild conditions.     

Solvent extraction and extraction–voltammetric determination of phenols using room temperature ionic liquid

The phenolic compounds phenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitrophenol, 1-naphthol, 2-naphthol, and 4-chlorophenol are extracted nearly quantitatively from aqueous solution into the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF₆) in molecular form at pH<pK_a. Picric acid is extracted efficiently in anionic form. Recovery of pyrocatechol and resorcinol is much lower. The effect of pH, phenol concentration, and volume ratio of aqueous and organic phases were studied. Ionic liquid BMImPF₆ is shown to be suitable for extraction–voltammetric determination of phenols without back-extraction or addition of support electrolyte. The electrochemical window of BMImPF₆ at various electrodes was determined, and voltammetric oxidation of phenols and reduction of nitrophenols in BMImPF₆ was studied.