Prediction of aqueous solubilities of solid carboxylic acids with COSMO-RS

The methodology for the prediction of aqueous solubilities of solid organic compounds, and their temperature dependence, based on the Conductor-like Screening Model for Real Solvents (COSMO-RS/COSMOtherm) procedure, is presented and evaluated. The predictive capability of the quantum chemistry based program and the applied methodology was tested on the most common solid carboxylic acids. From the temperature dependence of the solubilities, the mean apparent enthalpies of solution were derived. The results obtained for a set of 27 carboxylic acids, consisting of aromatic carboxylic acids, dicarboxylic acids, as well as hydroxycarboxylic acids, are in good agreement with the experimental solubility data and their dependence with the temperature. The mean apparent enthalpies of solution, although of the same order of magnitude of the experimentally values, seem to be systematically underestimated.     

Morphology and grafting of oxazoline-functional polymer particles with various carboxylic acids

Oxazoline-functionalized, crosslinked PMMA-particles, prepared by free radical nonaqueous dispersion polymerization, were grafted with n-decanoic acid and carboxylic acid-terminated polystyrene. Oxazoline groups, separated by an alkylspacer from the PMMA backbone, showed enhanced mobility with respect to the backbone, as evaluated by solid-state NMR spectroscopy using a dipolar filter. As a function of molecular mass of the carboxylic acid, the oxazoline conversion varied from 70 mol % for n-decanoic acid to 1% for monocarboxylate-terminated polystyrene CT-PS with M_n: 15,900 g/mol. Morphological studies, performed by TEM, showed that reaction with acid terminated polystyrene results exclusively in interfacial grafting at the particle surface. At low grafting levels a raspberry-like morphology was obtained, whereas grafting levels exceeding 14 wt % CT-PS resulted in core-shell morphology. Core-shell morphology was also verified by static light scattering using toluene solvent, which is isorefractive to the PMMA core. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1821–1827, 1998     

Silver-catalyzed decarboxylative alkynylation of aliphatic carboxylic acids in aqueous solution

C(sp(3))-C(sp) bond formations are of immense interest in chemistry and material sciences. We report herein a convenient, radical-mediated and catalytic method for C(sp(3))-C(sp) cross-coupling. Thus, with AgNO(3) as the catalyst and K(2)S(2)O(8) as the oxidant, various aliphatic carboxylic acids underwent decarboxylative alkynylation with commercially available ethynylbenziodoxolones in aqueous solution under mild conditions. This site-specific alkynylation is not only general and efficient but also functional group compatible. In addition, it exhibits remarkable chemo- and stereoselectivity.     

Silver-catalyzed decarboxylative fluorination of aliphatic carboxylic acids in aqueous solution

Although fluorinated compounds have found widespread applications in the chemical and materials industries, general and site-specific C(sp(3))-F bond formations are still a challenging task. We report here that with the catalysis of AgNO(3), various aliphatic carboxylic acids undergo efficient decarboxylative fluorination with SELECTFLUOR(?) reagent in aqueous solution, leading to the synthesis of the corresponding alkyl fluorides in satisfactory yields under mild conditions. This radical fluorination method is not only efficient and general but also chemoselective and functional-group-compatible, thus making it highly practical in the synthesis of fluorinated molecules. A mechanism involvinig Ag(III)-mediated single electron transfer followed by fluorine atom transfer is proposed for this catalytic fluorodecarboxylation.     

Association of carboxylic acids in aqueous solutions from conductivity data

Using precision conductivity data for aqueous carboxylic acid systems at 25 and 30°C, accurate thermodynamic ion association and dimerization equilibrium constants were determined. The data for formic, acetic, propionic and butyric acids are analyzed with the Fuoss-Hsia conductance equation as modified by Justice and Barthel. The treatment requires that triple ion formation is negligible.     

Peculiarities of catalytic behavior of bases in the reaction of aliphatic carboxylic acids with epoxide

A study was carried out on the kinetics of the reaction of 1-chloro-2,3-epoxypropane (epichlorohydrin, ECH) with aliphatic carboxylic acids in the presence of (3-chloro-2-hydroxypropyl)trimethylammonium (CHPTMA) chloride obtained by trimethylammonium chloride and ECH. We compared the catalytic activity of CHPTMA chloride, trialkylamines, and tetraalkylammonium halides and evaluated the effect of their structure. An ab initio quantum-chemical calculation was performed to obtain a detailed analysis of the state of the catalysts in this system in order to understand the peculiarities of catalytic activity of these bases. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 292–297, September–October, 2008.     

Rules governing vapor-phase extraction of carboxylic acids and phenols from aqueous solutions

The influence of the molecular structure of the components to be extracted and the type of the extractant used on the effectiveness of vapor-phase extraction from water was studied for the example of low-molecular-weight carboxylic acids C₂-C₆ and phenols. Extraction parameters were found to depend on the length of the analyte molecule and its polarity. The experimental data and correlations observed substantiated the validity of the suggested mechanism of vapor-phase extraction. Changes in the Gibbs energy of extraction equilibrium as the length of the analyte molecule (in the homologous series of organic acids C₂-C₆) and molecule polarity (for the example of cresol isomers) increased were evaluated.     

Distribution of carboxylic acids between water and nonpolar organic solvents

Equations which describe the distribution of carboxylic acids between water and nonpolar organic solvents, and which make allowance for their dimerization in the organic solvent, their association with water molecules, and the nonideal nature of the organic phase, have been examined. It has been shown that it is necessary to study the distribution of the carboxylic acid and water between the phases in order to determine the constants for the distribution, hydration, and dimerization of the carboxylic acids.     

The effect of extragent properties on the distribution of carboxylic acids

It has been established that the generalization of data on the distribution of carboxylic acids between organic and aqueous phases using the multiparameter linear free energy equations is preferential to using the London-Debye-Keesom potentials, which requires nonpolar and polar extragents to be examined separately. The formation of hydrogen bond between the components, which is determined by the basicity of an extragent, was shown to have an effect on the distribution value.     

Effect of pH on the viscosity of titanium dioxide aqueous dispersions with carboxylic acids

Dispersions of titanium dioxide nanoparticles with terephthalic acid, isophthalic acid, salicylic acid, benzoic acid, and pyridine-2,5-dicarboxylic acid were prepared by aqueous grinding. The pH of the dispersions was adjusted by adding either HCl or NaOH, and the viscosity of the dispersions was measured. It was found that the viscosity of the system depends strongly on pH. The qualitative interpretation of the results based on the DLVO theory is presented. The evidence of the effect of bridging interactions on the viscosity of titanium dioxide-dicarboxylic acid dispersions is discussed.     

Atomic layer deposition of organic-inorganic hybrid materials based on saturated linear carboxylic acids

Atomic layer deposition (ALD) has successfully provided thin films of organic-inorganic hybrid materials based on saturated linear carboxylic acids and trimethylaluminium (TMA). Films were grown for seven carboxylic acids: oxalic, malonic, succinic, glutaric, pimelic, suberic and sebacic acid, i.e. ranging from 2 to 10 carbon atoms in the molecular structure. These processes show exceptionally high growth rates; up to 4.3 nm/cycle for the pimelic acid-TMA system. Quartz crystal microbalance measurements of the growth dynamics indicate that all systems are of a self limiting ALD-type. Nevertheless, temperature dependent growth was observed in several systems. The width of the ALD windows shows correlations with the length of the carbon chains. Fourier transform infrared spectroscopy clearly proved that the deposited films are of a hybrid character, where the carboxylic acids primarily form bidentate complexes, though bridging complexes may also form. All films are X-ray amorphous as deposited. The films were further analyzed by atomic force microscopy for surface roughness and topography, UV-Vis spectroscopy and ellipsometry for optical properties, and the goniometer method for measuring sessile drops for surface wetting properties. Apart from the oxalic and malonic acid-TMA systems, the films are stable in contact with water. The films are generally smooth, transparent and have a refractive index close to 1.5. The complete coverage and accurate growth control offered by the ALD technique is here proven to provide surface-functionalized hybrid materials resembling metal-organic frameworks (MOF), probably as rather dense structures, yet with substantial potential for applications.     

Solvation of amides of carboxylic acids in aqueous solutions of ethylene glycol

Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg^–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.     

Synthesis and properties of silicon- and germanium-containing α-acetylenic carboxylic acids

Conclusions Some previously unknown Si- and Ge-containing-acetylenic carboxylic acids were synthesized and their decarboxylation was studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 189–192, January, 1977.     

Preparation and properties of pure lithio esters of some carboxylic acids

Lithio esters of carboxylic acids have been prepared in pure state and their properties are described. Interaction between the lithio esters with alkali metals alkoxides has been demonstrated, and some adducts have been isolated. The IR and UV spectra of these compounds are described, and their structures are discussed.     

Relationship between chromatographic properties of aromatic carboxylic acids and their structure

The retention of aromatic carboxylic acids and their esters in reversed-phase HPLC is proportional to the sum of their partition coefficients in octanol-water system and retention increments. This equation can be used for the identification of various side-products formed in monomer production.     

Influence of branching architecture on polymer properties

Hyperbranched polymers (HBPs), invented at the end of 1980s, are one important subclass of the fourth generation macromolecular architectures following the linear, branched, and crosslinking polymers. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. HBPs are composed of linear units, dendritic units, and terminal units. The degree of branching (DB), a term to describe the composition of these three structure units and thus the branching architecture of polymers, is one of the most important intrinsic parameters for HBPs. This review has summarized the effect of the DB on the physical and chemical properties of HBPs, including the rheological property, crystallization and melting behaviors, glass transition, thermal and hydrolytic degradations, phase characteristics, lower critical solution temperature phase transition, optoelectronic properties, encapsulation capability, self‐assembly behavior, biomedical applications, and so on. Such a structure and property relationship will build a bridge between the syntheses and applications of HBPs, especially in the application areas of functional materials, biomedical materials, and nanotechnology. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1277–1286, 2011     

Modeling the properties of self-assembled monolayers terminated by carboxylic acids

Self-assembled monolayers of long-chain carboxylic acids are often used as substrates to promote the growth of oriented crystals. Recent work has shown that the length of the chain (odd or even number of carbon atoms) determines whether oriented growth is observed. We use molecular dynamics simulations to investigate whether the configuration of the headgroups is significantly different in the two cases. We conclude that there are differences between odd- and even-length chains, even at 300 K and in the presence of water for some packings of the monolayer. We discuss whether these differences are large enough to account for the different behavior.     

Effect of cyclodextrins on the rhodium-catalysed hydrogenation of unsaturated carboxylic acids in water

Addition of cyclodextrin to the well-known RhCl₃/TPPTS (trisulfonated triphenylphosphine) hydrogenation catalytic system leads to high selectivities in the hydrogenation of unsaturated carboxylic acids in water. The presence of both cyclodextrin and sulfonate ions is required to obtain high selectivities.     

NIR spectroscopic properties of aqueous acids solutions

Acid content is one of the important quality attributes in determining the maturity index of agricultural product, particularly fruits. Despite the fact that much research on the measurement of acidity in fruits through non-destructive spectroscopy analysis at NIR wavelengths between 700 to 1,000 nm has been conducted, the same response towards individual acids is not well known. This paper presents NIR spectroscopy analysis on aqueous citric, tartaric, malic and oxalic solutions through quantitative analysis by selecting a set of wavelengths that can best be used to measure the pH of the solutions. The aquaphotomics study of the acid solutions has generated R2 above 0.9 for the measurement of all acids. The most important wavelengths for pH are located at 918-925 nm and 990-996 nm, while at 975 nm for water.     

Thermodynamic parameters for the protonation of carboxylic acids in aqueous tetraethylammonium iodide solutions

The protonation constants of 21 carboxylic acids (formic, acetic, propionic, benzoic, phenoxyacetic, salicylic, oxalic, malonic, succinic, itaconic, malic, tartaric, oxydiacetic, thiodiacetic, thiodipropionic, phthalic, maleic, citric, 1,2,3-tricarboxylic, 1,2,4-tricarboxylic and 1,2,4,5-tetracarboxylic), have been determined potentiometrically, by pH-metric measurements, at several temperatures and ionic strengths, 5T55°C, 0<11 mol-dm^–3, using tetraethylammonium iodide as background salt. General equations for the dependence on ionic strength of thermodynamic parameters have been found. The statistical significance of results and the possibility of using a simple model for the thermodynamics of carboxylic acids protonation, is discussed.