Comparative Study on Reactive Extraction of Picolinic Acid with Six Different Extractants (Phosphoric and Aminic) in Two Different Diluents (Benzene and Decan-1-ol)

The equilibrium study on reactive extraction of picolinic acid by six different extractants (phosphoric and aminic) dissolved in two different diluents (benzene and decane-1-ol) is carried out to evaluate the performance of extractants and diluents. The extraction ability in terms of the distribution coefficient (K _D) is found to be in the order of tri-n-octylamine (TOA) ≥ tri-n-dodecylamine (TDDA) > di-2-ehylhexyl phosphoric acid (D2EHPA) > tri-n-butyl phosphate (TBP) > tri-octyl methyl ammonium chloride (Aliquat 336) > tri-n-octyl phosphine oxide (TOPO) with both diluents. Decan-1-ol is found to be the better solvating medium for the acid-extractant complexes. A mathematical model based on mass action law is employed to estimate the values of partition coefficient (P) and dimerization constant (D) in physical extraction, and equilibrium extraction constants (K _E) in chemical extraction. The values of loading ratios (Z) less than 0.5 imply the formation of (1:1) acid:extractant solvates in the organic phase. Decan-1-ol with TOA is the most effective solvation medium with K _{D, max} = 9 at 0.01 kmol · m^?3 of picolinic acid and K _E = 19.448 m³ · kmol^?1.     

稀释剂对三辛胺萃取羧酸的影响

研究了三辛胺萃取羧酸过程的机理,发现该过程中稀释剂的影响十分显著,在不同的稀释剂中三辛胺萃取羧酸的分配比相差三十至七十倍。其萃取能力与三辛胺的浓度和稀释剂的性质有关。萃取剂浓度一定时,取决于萃合物与稀释剂的相互作用能力及其在稀释剂中的疏溶作用。相互作用能力越强,疏溶作用越弱,越有利于革取。     

Enantioselective Ring Opening Reactions of Azabenzonorbornadienes with Carboxylic Acids

The palladium/silver (Pd/Ag) co‐catalytic system was found to be effective for the enantioselective ring opening reactions of the low reactive azabenzonorbornadienes with weak nucleophilic carboxylic acids. Both aryl and alkyl carboxylic acids are suitable nucleophiles and afforded the cis ring opening products in good yields with excellent enantioselectivities. The absolute configuration of one of the products has been confirmed by X‐ray crystal structure analysis, and a plausible reaction pathway is proposed.

     

Lewis Acids as Highly Efficient Catalysts for the Decarboxylative Esterification of Carboxylic Acids with Dialkyl Dicarbonates

Mild Lewis acids such as Mg(ClO₄)₂ show a new level of catalytic activity for the decarboxylative esterification of carboxylic acids with commercially available dialkyl dicarbonates. In the presence of as little as one mol % Mg(ClO₄)₂ catalyst, carboxylic acids can thus easily and near quantitatively be protected at room temperature, e.g., as methyl, benzyl, or t‐butyl esters. Only volatile by‐products are released so that the purification of the products is particularly easy. Many sensitive functionalities are tolerated, including even phenol esters, or free hydroxy and BOC groups.     

Fractionation of Carboxylic Acids Mixture Obtained by Succinic Fermentation using Reactive Extraction

Formic, acetic, and succinic acids have been selectively separated from their mixture obtained by A. succinogenes fermentation using reactive extraction with tri-n-octylamine (TOA) dissolved in three solvents with different polarities (n-heptane, butyl acetate, and dichloromethane) without and with 1-octanol addition. This technique allows recovering formic and acetic acids from the mixture, the raffinate containing only succinic acid. The extractant concentration and organic phase polarity control the selectivity of acids extraction. Thus, at pH = 1, the selectivity factor increased from 92, in the absence of 1-octanol; to 148, in the presence of this alcohol in organic phase. The corresponding optimum concentrations of TOA in the solvent were 30 and 50 g/l, respectively. The total separation of monocarboxylic acids from the mixture with succinic acid is possible by a multi-stage extraction process, adjusting the extractant concentration in each stage to that stoechiometrically needed for reactions with formic and acetic acids only. The addition of 1-octanol reduces the number of required extraction stages.     

HOFs Built from Hexatopic Carboxylic Acids: Structure,Porosity, Stability,and Photophysics

Hydrogen-bonded organic frameworks (HOFs) have attracted renewed attention as another type of promising candidates for functional porous materials. In most cases of HOF preparation, the applied molecular design principle is based on molecules with rigid π-conjugated skeleton together with more than three H-bonding groups to achieve 2D- or 3D-networked structures. However, the design principle does not always work, but results in formation of unexpected structures, where subtle structural factors of which we are not aware dictate the entire structure of HOFs. In this contribution, we assess recent advances in HOFs, focusing on those composed of hexatopic building block molecules, which can provide robust frameworks with a wide range of topologies and properties. The HOFs described in this work are classified into three types, depending on their H-bonded structural motifs. Here in, we focus on: (1) the chemical aspects that govern their unique fundamental chemistry and structures; and (2) their photophysics at the ensemble and single-crystal levels. The work addresses and discusses how these aspects affect and orient their photonic applicability. We trust that this contribution will provide a deep awareness and will help scientists to build up a systematic series of porous materials with the aim to control both their structural and photodynamical assets.     

Rhodium‐Catalyzed Decarbonylative Direct Olefination of Arenes with Vinyl Carboxylic Acids

A rhodium(I)‐catalyzed direct C H bond olefination of pyridyl‐substituted arenes with readily available vinyl carboxylic acids has been realized. This reaction occurred efficiently without the need for any external oxidant, affording the ortho‐olefinated products in high yields and excellent regioselectivities. Diversely substituted vinyl carboxylic acids behaved as efficient olefination reagents under the reaction conditions, and a range of functional groups in both coupling partners was well tolerated. Mechanistic studies indicated that a decarbonylation step is involved in this catalytic process, and pivalic anhydride [(t‐BuCO)₂O] acts as the activator of the carboxylic acids for the in situ generation of highly active anhydrides.

     

黄酮羧酸类化合物合成与生物活性研究进展

天然的黄酮类化合物一般不具有羧基,但在黄酮类化合物上引入羧基,便具有特殊的生理活性,这大大丰富了黄酮类化合物的家族,拓展了黄酮类化合物的应用范围及提高黄酮类化合物的生理活性。文章综述了黄酮羧酸类化合物的合成方法及其生理活性进展。     

Bimetallic‐Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols

The homogeneously catalyzed reduction of carboxylic acids with hydrogen was studied. Bimetallic catalysts consisting of a group 8 or 9 late transition‐metal and a second group 6 or 7 transition‐metal carbonyl showed a synergistic effect allowing the conversion in good yields under moderate conditions. Besides the effect of different catalyst precursors, the influence of temperature, hydrogen pressure, and catalyst concentration was investigated. An equimolar mixture of [Rh(acac)(CO)₂] and [Mo(CO)₆] showed the highest activity and was therefore applied to the reduction of lactones to diols. The reduction potential of the catalyst was found to be dependent on the ring size of the lactone used. Five‐membered ring lactones were hardly converted to diols whereas six‐ and seven‐ membered ring lactones reacted easily.     

Palladium‐Catalyzed Reduction of Carboxylic Acids to Aldehydes with Hydrosilanes in the Presence of Pivalic Anhydride

A palladium catalyst system that allows the reduction of carboxylic acids to the corresponding aldehydes with hydrosilanes as reducing agent and pivalic anhydride as an indispensable reagent has been developed. A simple mixture of commercially available bis(dibenzylideneacetone)palladium(0) [Pd(dba)₂], tri(para‐tolyl)phosphane and methylphenylsilane realized the reduction of various aliphatic carboxylic acids as well as benzoic acids to aldehydes in good to high yields.

     

Direct Catalytic Formation of Primary and Tertiary Amides from Non‐Activated Carboxylic Acids,Employing Carbamates as Amine Source

The operationally simple titanium(IV)‐ or zirconium(IV)‐catalyzed direct amidation of non‐activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N‐dimethyl‐substituted amides in good to excellent yields.     

Reactive solvent extraction of amino acids with cationic extractants

A mixture of amino acids (arginine, phenylalanine, alanine, glycine and aspartic acid) in solution was extracted by four acidic extractants (dinonylnaphthalenesulphonic acid (DNNSA), di(2-ethylhexyl)monothiophosphoric acid (D2EHPA(S)), di(2-ethylhexyl)phosphoric acid (D2EHPA) and Versatic 10) in toluene. The extractive capacity of the organic phase for the amino acids, using DNNSA, D2EHPA(S) and D2EHPA was found to decrease in the order arginine>phenylalanine>alanine>glycine>aspartic acid, although at low pH values phenylalanine>arginine occurred for D2EHPA(S) and D2EHPA. Separation factors derived for pairs of amino acids were in the range 2·0 (glycine–aspartic acid) to 20·1 (alanine–glycine). The extractive and loading capability of the extractants for the amino acids was found to decrease in the order DNNSA>D2EHPA(S)>D2EHPA>Versatic 10, which follows the reverse order of their respective acid dissociation constants. DNNSA was shown to be a promising extractant for the extraction and fractionation of amino acids. © 1998 SCI     

Improving Properties of Starch-Based Adhesives with Carboxylic Acids and Enzymatically Polymerized Lignosulfonates

A novel strategy for improving wet resistance and bonding properties of starch-based adhesives using enzymatically polymerized lignosulfonates and carboxylic acids as additives was developed. Therefore, lignosulfonates were polymerized by laccase to a molecular weight of 750 kDa. Incorporation of low concentrations (up to 1% of the starch weight) of 1,2,3,4-butanetetracarboxylic acid (BTCA) led to further improvement on the properties of the adhesives, while addition of greater amounts of BTCA led to a decrease in the properties measured due to large viscosity increases. Great improvements in wet-resistance from 22 to 60 min and bonding times (from 30 to 20 s) were observed for an adhesive containing 8% enzymatically polymerized lignin and 1% BTCA. On the other hand, the addition of citric acid (CA) deteriorated the properties of the adhesives, especially when lignosulfonate was present. In conclusion, this study shows that the addition of the appropriate amount of enzymatically polymerized lignosulfonates together with carboxylic acids (namely BTCA) to starch-based adhesives is a robust strategy for improving their wet resistance and bonding times.     

Triphenylphosphine‐Catalyzed Dehydrogenative Coupling Reaction of Carboxylic Acids with Silanes – A Convenient Method for the Preparation of Silyl Esters

Triphenylphosphine has been found to be an efficient catalyst for the dehydrosilylation of carboxylic acids with silanes. In the presence of 4 mol % of triphenylphosphine (PPh₃), dehydrosilylation reactions in DMF afforded the corresponding silyl esters at 120 °C in good yield.     

Partitioning of Carboxylic Acid between Oil and Water Phases. Experimental,Correlation, and Prediction

Partition coefficients for the carboxylic acids (A) acetic and formic acids between oil and water were measured, correlated, and predicted. The experiments were conducted by equilibrating the systems, soybean oil (SO)–H₂O–A and fatty acid methyl ester (FAME)–H₂O–A, at 40 °C employing different compositions. The partition coefficients were correlated using the UNIQUAC model and, also, predicted by calculating the activity coefficients of the carboxylic acid in the two phases using a group contribution method, the UNIFAC equation. Agreement of experimental partition coefficients values with those estimated by UNIFAC are fair. Other experimental data from literature were also correlated and are discussed.     

Iron‐Catalyzed Oxidative Cleavage of Olefins and Alkynes to Carboxylic Acids with Aqueous tert‐Butyl Hydroperoxide

A new method for the oxidation of aromatic olefins and alkynes has been developed using inexpensive iron(III) chloride hexahydrate (FeCl₃⋅6 H₂O, 5 mol%) catalyst in combination with commercially available aqueous 70% tert‐butyl hydroperoxide (TBHP) as oxidant. The present system works well for aromatic alkenes and alkynes with both electron‐donating and electron‐withdrawing substituents being tolerated. The protocol is free from chromatographic purification and the carboxylic acids are obtained in high yields by simple filtration.     

Direct Condensation of Carboxylic Acids with Alcohols: The Atom Economic Protocol Catalysed by Fe3+-Montmorillonite

Fe³⁺-montmorillonite clay catalyst was used for the first time to esterify various aliphatic, aromatic, ,-unsaturated mono- and di-carboxylic acids and long chain fatty acids with alcohols under mild reaction conditions in good to excellent yields. The present heterogeneous catalytic system is a potential candidate not only for laboratory practice but also for commercial application and offers an environmentally safer alternative to the existing processes.     

Extraction of Benzene and Naphthalene Carboxylic Acids Using Quaternary Ammonium Salts As a Model Study for the Separation of Coal Oxidation Products

Abstract

The ion‐pair solvent extraction of benzene‐ and naphthalene‐carboxylic acids has been investigated as a model study for the separation of coal oxidation products, which are formed by treatment with alkaline solutions at high temperatures. It was possible that benzene‐ and naphthalene‐dicarboxylic acids are extracted into several types of organic solvents with quaternary ammonium ions. The extraction equilibrium constants (K_ex) for benzoic acid, 1,2‐benzenedicarboxylic acid, 1,3‐benzenedicarboxylic acid, 1‐naphthoic acid, 2‐naphthoic acid, 2,3‐naphthalenedicarboxylic acid, and 2,6‐naphthalenedicarboxylic acid into chloroform were determined at 20°C. The difference of K_ex among the aromatic acids was sufficiently large for designing a separation method for these aromatic acids. It was unexpected that the extraction of dicarboxylic acids was slower than that of monocarboxylic acids, although the ion‐pair formation of aromatic carboxylate ion with quaternary ammonium ion is normally considered as a diffusion control reaction in aqueous phase. Thus, this fact suggests that the phase transfer of the ion‐pair from aqueous to organic phase is the rate‐determining step. Liner‐free‐energy relationship was observed for the monocarboxylic acids using different quaternary ammonium salts while that was ambiguous for the dicarboxylic acids. This is due to the steric influence of the counter ions for the magnitude of K_ex.     

Copper‐Catalyzed Decarboxylation of Aromatic Carboxylic Acids: En Route to Milder Reaction Conditions

The copper‐catalyzed decarboxylation of carboxylic aromatic acids has been advantageously achieved by using aliphatic amines like tetramethylethylenediamine (TMEDA) or hexamethylenetetraamine (HMTA) as ligands instead of the aromatic heterocyclic amines (quinoline, phenanthroline) used until now. The improvement is significant since the reaction can be performed at a lower temperature (ca. 50 °C less) and the reaction time is clearly shorter (15 min instead of 12 to 24 h).