Carbonic Acid Derivatives Research Articles

SYNTHESIS AND ANALYSIS OF COORDINATION COMPOUNDS OF NICKEL(II) ACETATE WITH MONOETHANOLAMINE AND p-NITROBENZOIC ACID

This article clarifies the synthesis of a complex combination of p-nitrobenzoic acid with Ni2+ from aromatic carbonic acid derivatives. Moreover, factors influencing the synthesis of the complex compound under room conditions were identified. In particular, the time dependence of the reaction, the effect of temperature, the concentration dependence were studied in practice. The synthesized complex was studied using IR-Fourier spectrometry, elemental analysis, mass spectrometry, TG-DSK and X-ray structural analysis, its chemical structure was determined, and this new complex was proved to be thermally and chemically stable

Manganese-catalyzed hydroboration of carbon dioxide and other challenging carbonyl groups

Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and ultimately in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals. In particular, it can open novel pathways for the valorization of non-fossil feedstocks. Catalysts based on earth-abundant, cheap, and benign metals would greatly contribute to the development of sustainable synthetic processes derived from this concept. Herein, a manganese pincer complex [Mn(Ph2PCH2SiMe2)2NH(CO)2Br] (1) is reported to enable the reduction of a broad range of carboxylic acids, carbonates, and even CO2 using pinacolborane as reducing agent. The complex is shown to operate under mild reaction conditions (80–120 °C), low catalyst loadings (0.1–0.2 mol%) and runs under solvent-less conditions. Mechanistic studies including crystallographic characterisation of a borane adduct of the pincer complex (1) imply that metal-ligand cooperation facilitates substrate activation.

Synthesis and film formation of furfuryl- and maleimido carbonic acid derivatives of dextran

Carbonic acid derivatives of dextran possessing furfuryl- and maleimido moieties were synthesized and processed into thin films by spin coating. First, products with different degrees of substitution (DS) of up to 3.0 and substitution patterns were obtained and characterized by NMR- and FTIR spectroscopy, as well as elemental analysis. Thin films possessing maleimide groups were obtained by spin coating of maleimido dextran (furan-protected) and dextran furfuryl carbamate that was converted with bismaleimide. The removal of the protecting group (furan) on the thin film was monitored by QCM-D and compared with gravimetric analysis of the bulk material. Film morphology and wettability were determined by means of AFM and contact angle measurements.

ChemInform Abstract: Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide.

The chemoselective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six-membered cyclic carbonates remains a challenging topic. Here, an effective method for their synthesis relying on the use of Al catalysis is described. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2- and 3-position(s) of the oxetane ring. The presented methodology is the first general approach towards the formation of six-membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six-membered cyclic carbonates, also the unprecedented room-temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five- and six-membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.

Polyurethane elastomers based on carbonic and tartaric acid derivatives as renewable resources

In the present study, three methods of introduction of the tartaric acid derivative into poly(car- bonate-urethane)s chemical structure are presented and discussed. Tartaric acid derivative containing two free and two protected OH groups was introduced according to polycondensation, ring opening polymerization (in oligocarbonate synthesis step) and polyaddition (in prepolymer synthesis step as a chain extender) reactions. The prepared poly(carbonate-urethane)s were characterized by NMR and FT-IR spectroscopies, DSC and TGA thermal analyses, and mechanical properties measurements. The in- fluence of the introduced tartaric acid derivative on properties of oligocarbonates and polyurethanes was investigated.

Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide.

The chemoselective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six-membered cyclic carbonates remains a challenging topic. Here, an effective method for their synthesis relying on the use of Al catalysis is described. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2- and 3-position(s) of the oxetane ring. The presented methodology is the first general approach towards the formation of six-membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six-membered cyclic carbonates, also the unprecedented room-temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five- and six-membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.

ChemInform Abstract: Iron‐Catalyzed Reduction of Carboxylic and Carbonic Acid Derivatives

AbstractReview: 89 refs.

ChemInform Abstract: Highly Versatile Catalytic Hydrogenation of Carboxylic and Carbonic Acid Derivatives Using a Ru‐Triphos Complex: Molecular Control over Selectivity and Substrate Scope.

ChemInform Abstract: Highly Versatile Catalytic Hydrogenation of Carboxylic and Carbonic Acid Derivatives Using a Ru‐Triphos Complex: Molecular Control over Selectivity and Substrate Scope.

Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex: molecular control over selectivity and substrate scope.

The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H2] or the cationic intermediate [Ru(Triphos)(Solvent)(H)(H2)](+) in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to C═O groups and C-O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H2] and [Ru(Triphos)(μ-H)]2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources.

ChemInform Abstract: Catalytic Reductive Transformations of Carboxylic and Carbonic Acid Derivatives Using Molecular Hydrogen

AbstractReview: 227 refs.

Catalytic Reductive Transformations of Carboxylic and Carbonic Acid Derivatives Using Molecular Hydrogen

A comprehensive overview on homogeneous catalytic hydrogenation of carboxylic acids and its derivatives as well as carbonic acid derivatives with transition metal-based molecular catalysts is described. Despite the tremendous potential in the hydrogenation of these less electrophilic carbonyl compounds using molecular hydrogen in synthetic organic chemistry, their reduction still relies mostly on the stoichiometric use of metal hydride reagents, such as LiAlH4, NaBH4, and their derivatives. For the past decade, a significant and rapid progress in particularly ester hydrogenation has been achieved by utilization of conceptually new bifunctional molecular catalysts originating from the metal–ligand cooperation effects. The bifunctional-catalyst-promoted hydrogenation using molecular hydrogen is now realized to be a practical tool in synthetic organic chemistry in both academia and industry. The industrial outlook for the present hydrogenation is bright because of its operational simplicity, scope, economic viability, and growing awareness of the need for green chemistry.

Segmental copolymers of condensation polyesters and polylactide

L-Lactide (LA) polymerizations carried out in the presence of various types of polyesterodiols and polyesterocarbonatediols obtained from 1,4-butanediol, 1,3-propanediol and dimethyl esters of adipic, terephthalic and carbonic acids were studied. It was found, based on 1H NMR and MALDI ToF analysis of the chains microstructure that the reactions carried out in bulk at 190 °C in the presence of tin (II) 2-ethylhexanoate as a catalyst led to the formation of a mixture of polylactide (PLLA) and block copolymers of LA with the applied macrodiols with high yield. DSC studies of the obtained products indicate that the segments comprising of adipic and carbonic acid derivatives were fully miscible with PLLA causing the reduction of its glass transition temperature. The segments containing terephthalic acid monomeric units in its structure showed only slight miscibility with PLLA segments and the obtained products consist of two phases of glass transition temperatures close to those of PLLA and the macrodiol. These systems are characterized by better thermal stability and higher elasticity than PLLA.

ChemInform Abstract: Synthesis of Alkyl‐ and Cycloalkylamines by Reduction of Carbonic and Carboxylic Acid Derivatives

AbstractReview: 257 refs.

ChemInform Abstract: Investigations on 1,3-Thiazines. Part 40. Iminium Carbonic Acid Derivative Salts. Part 4. Cyclic Ketene S,N-Acetals from Iminium Thiocarbonic Acid Ester Chlorid - Chlorides and Doubly Activated Cyclic Methylene Compounds.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Acylation of N-(2,6-Dimethylphenyl)-α-alanine Methyl Ester with sp-Hybridized Carbonic Acid Derivatives.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Hydrophobically Functionalized Chitosan Particles

Particles of chitosan have a very polar surface, and thus they are easily wetted by water and also dissolve in acidic media. The hydroxyl and amino groups offer a high potential for grafting reactions. Aldehydes and carbonic acid derivatives were covalently grafted, preferably onto the amino groups. The reactions were carried out in solution as homogeneous phase reactions as well as on the particle surfaces as heterogeneous phase reactions. Covalently bonded alkyl chains impart the chitosan molecules with hydrophobic properties. We employed different methods such as NMR, XPS, elemental analysis and FT-IR spectroscopy to study the reactions and to estimate the degree of functionalization. The wetting behavior of the particles was investigated by a modified Wilhelmy technique, where an adhesive tape completely coated with the particles was dipped in water. Some of the samples having a high degree of functionalization showed super-hydrophobic surface properties. The observed super-hydrophobic effect results from a combination of the hydrophobic properties of the modified particles and the roughness of the particle coating.

ChemInform Abstract: Carboxylic Acid Esters: Synthesis from Carbonic Acid Derivatives

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Carboxylic Acids — Synthesis from Carbonic Acid Derivatives

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Amides from Carbonic Acid Derivatives

AbstractFor Abstract see ChemInform Abstract in Full Text.

Novel Substrates for Palladium‐Catalyzed Coupling Reactions of Arenes

AbstractFor Abstract see ChemInform Abstract in Full Text.