Activity coefficients for liquid organic reactions : towards a better understanding of true kinetics with the synthesis of jasmin aldehyde as showcase

The aldol condensation of benzaldehyde and heptanal is taken as an example of reversible liquid phase organic reactions to show that inclusion of activity coefficients reveal distinct differences in conversion and product distribution when different solvents methanol, ethanol, n-propanol, or n-butanol are used. The purpose of this work is to show a pronounced solvent effect for a given set of identical kinetic parameters, i.e., the same liquid phase kinetics can result in different conversion and yield values, depending on the choice of solvent. It was shown that subsequent parameter estimation without inclusion of the activity coefficients resulted in a pronounced deviation from the true' kinetics, up to a factor of 30. It is proposed that the usage of average activity coefficients gives already a significant improvement, resulting in acceptable parameter estimates

Forging Fluorine-Containing Quaternary Stereocenters by a Light-Driven Organocatalytic Aldol Desymmetrization Process

Reported herein is a light-triggered organocatalytic strategy for the desymmetrization of achiral 2-fluoro-substi- tuted cyclopentane-1,3-diketones. The chemistry is based on an intermolecular aldol reaction of photochemically generated hydroxy-o-quinodimethanes and simultaneously forges two adjacent fully substituted carbon stereocenters, with one bearing a stereogenic carbon–fluorine unit. The method uses readily available substrates, a simple chiral organocatalyst, and mild reaction conditions to afford an array of highly function- alized chiral 2-fluoro-3-hydroxycyclopentanones

Vinylogous aldol reaction of heterocyclic silyloxy dienes. Application in synthesis

A versatile, readily accessible triad of 2-enoxy silane synthons derived from furan, pyrrole, and thiophene is presented. These heterocycles, in reacting with carbonyl and carbonyl- related acceptors, act as vinylogous nucleophile modules, giving rise to diverse, functionality- rich, γ-substituted α,β-unsaturated carbonyl constructs. These, in turn, are invaluable platforms onto which further functional elements and chirality may be introduced. A couple of appealing applications—the variable construction of a repertoire of carbasugars and a library of annonaceous acetogenin segments—have been chosen to illustrate the viability of this vinylogous aldol approach

Surface intermediate species of the 4-isobutylacetophenone adsorption-reaction over fosfotungstic Wells-Dawson heteropoly acid

Surface adsorbed species of isobutylbenzene and 4-isobutylacetophenone on bulk fosfotungstic Wells-Dawson acid have been screened in the present investigation. The evolution of chemisorbed species towards products was followed through infrared spectroscopy of systems containing liquid reactants and the solid acid kept at various temperatures. Isobutylacetophenone adsorbs on Brønsted acid sites of the heteropoly acid and further reacts towards a condensation product similarly to the reaction of acetophenone over other acid materials such as, mordenite, niobic acid and sulfated zirconia. The condensation product possesses well defined infrared signals at 1654 cm-1 and 1597 cm-1 that resemble the carbonyl stretching vibration and the double bond of dypnone. Additional signals at 1221 cm-1 give more evidences of the formation of a chalcone type compound. A reaction mechanism of the Aldol condensation of 4-isobutylacetophenone through an enol reactive intermediate is proposed.Fil: Matkovic, Silvana Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Valle, Graciela Manuela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Briand, Laura Estefania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentin

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed

Reactive processing of formaldehyde and acetaldehyde in aqueous aerosol mimics: Surface tension depression and secondary organic products

The reactive uptake of carbonyl-containing volatile organic compounds (cVOCs) by aqueous atmospheric aerosols is a likely source of particulate organic material. The aqueous-phase secondary organic products of some cVOCs are surface-active. Therefore, cVOC uptake can lead to organic film formation at the gas-aerosol interface and changes in aerosol surface tension. We examined the chemical reactions of two abundant cVOCs, formaldehyde and acetaldehyde, in water and aqueous ammonium sulfate (AS) solutions mimicking tropospheric aerosols. Secondary organic products were identified using Aerosol Chemical Ionization Mass Spectrometry (Aerosol-CIMS), and changes in surface tension were monitored using pendant drop tensiometry. Hemiacetal oligomers and aldol condensation products were identified using Aerosol-CIMS. Acetaldehyde depresses surface tension to 65(\pm2) dyn/cm in pure water (a 10% surface tension reduction from that of pure water) and 62(\pm1) dyn/cm in AS solutions (a 20.6% reduction from that of a 3.1 M AS solution). Surface tension depression by formaldehyde in pure water is negligible; in AS solutions, a 9% reduction in surface tension is observed. Mixtures of these species were also studied in combination with methylglyoxal in order to evaluate the influence of cross-reactions on surface tension depression and product formation in these systems. We find that surface tension depression in the solutions containing mixed cVOCs exceeds that predicted by an additive model based on the single-species isotherms.Comment: Published in Atmospheric Chemistry and Physics 22 November 201

Model studies on the pattern of volatiles generated in mixtures of amino acids, lipid oxidation-derived aldehydes, and glucose

The development of flavor and browning in thermally treated foods results mainly from the Maillard reaction and lipid degradation but also from the interactions between both reaction pathways. To study these interactions, we analyzed the volatile compounds resulting from model reactions of lysine or glycine with aldehydes originating from lipid oxidation [hexanal, (E)-2-hexenal, or (2E,4E)-decadienal] in the presence and absence of glucose. The main reaction products identified in these model mixtures were carbonyl compounds, resulting essentially from amino-acid-catalyzed aldol condensation reactions. Several 2-alkylfurans were detected as well. Only a few azaheterocyclic compounds were identified, in particular 5-butyl-2-propylpyridine from (E)-2-hexenal model systems and 2-pentylpyridine from (2E,4E)-decadienal model reactions. Although few reaction products were found resulting from the condensation of an amino acid With a lipid-derived aldehyde, the amino acid plays an important role in catalyzing the degradation and further reaction of these carbonyl compounds. These results suggest that amino-acid-induced degradations and further reactions of lipid oxidation products may be of considerable importance in thermally processed foods

Design and Synthesis of Oxazoline-Based Scaffolds for Hybrid Lewis Acid/Lewis Base Catalysis of Carbon–Carbon Bond Formation

A new class of hybrid Lewis acid/Lewis base catalysts has been designed and prepared with an initial objective of promoting stereoselective direct aldol reactions. Several scaffolds were synthesized that contain amine moieties capable of enamine catalysis, connected to heterocyclic metal-chelating sections composed of an oxazole–oxazoline or thiazole–oxazoline. Early screening results have identified oxa­zole–oxazoline-based systems capable of promoting a highly diastereo- and enantioselective direct aldol reaction of propionaldehyde with 4-nitrobenzaldehyde, when combined with Lewis acids such as zinc triflate