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Vibrational relaxation of matrix-isolated carboxylic acid dimers and monomers.
2009
Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrati…
Manganese(III)-mediated oxidative carbon-carbon bond cleavage of the 1,10-phenanthroline-5,6-dione ligand
1999
[EN] A new manganese(III)-1,10-phenanthroline-5,6-dione (phendione) complex possessing a putative Mn-2(mu-O) (mu-O2CMe)(2) core has been found to undergo a Ligand-based oxidative cleavage of the C(5)-C(6) bond in weak acid aqueous MeOH under aerobic conditions at room temperature to yield 2,2'-bipyridyl-3,3'-dicarboxylate with co-reduction to the corresponding Mn-II-phendione species.
Carboxylation of a linear low density polyethylene via gamma irradiation in presence of carbon dioxide in subcritical and supercritical conditions
1994
Abstract In this work the molecular modifications induced in a linear low density polyethylene gamma irradiated in presence of carbon dioxide both in subcritical and supercritical conditions are presented. The obtained results indicate that this process can be a new and interesting way in order to graft oxidized groups in the polyethylene chains. Moreover it is worth noting that, together with these functionalization reactions, also a significant crosslinking occurs, with improvement in some mechanical tensile behaviour.
Electrocarboxylation of aromatic ketones: Influence of operative parameters on the competition between ketyl and ring carboxylation
2007
Abstract The purpose of this work is to investigate the effect of operational parameters on the competition between the formation of the target 2-hydroxy-2-arylpropanoic acid and ring carboxylation in the electrocarboxylation of aromatic ketones. For the investigated ketones, this competition has been found to be dramatically influenced by different parameters such as the water content and the ratio between the carbon dioxide and the ketone concentrations (q = [CO2]/[ketone]). In particular, the target carboxylic acid formation can be favoured with respect to ring carboxylation by operating at high q ratios or by addition of small amounts of H2O to the reaction medium. An increase of the wa…
Electrochemical Oxidation of Carboxylic Acids in Water at Boron-Doped Diamond (BDD) Anodes in the Range of Potential of Oxygen Evolution: Detection M…
2013
The electrochemical oxidation in water solutions of selected carboxylic acids (namely oxalic, formic, acetic, maleic, and succinic) at boron-doped diamond (BDD) anodes was investigated by polarization and chronoamperometric measurements. In the presence of low concentrations of carboxylic acids, current densities changed approximately linearly with the acid concentrations. Furthermore, when the current densities were plotted as a function of the chemical oxygen demand, a similar response was observed for all the investigated acids with the exception of oxalic acid. For high carboxylic acid concentrations, the linear variation is often loosen and different behaviors are observed depending on…
Chemistry with Roataxanes: Intra- and Intermolecularly Covalently Linked Rotaxanes
2006
The direct introduction of sulfonamide units (cf. 9) into carboxamide-based rotaxanes allows us to intramolecularly bridge the “wheel” and the “axle” of such species for the first time as is shown by the bridged bissulfonamide rotaxane 11. Due to its stronger acidity the SO2-NH proton can be selectively abstracted by mild bases even in the presence of CO.NH and then be substituted by treatment with suitable iodo compounds. This leads intramolecularly to 11 (71% yield) and intermolecularly to bis[2]rotaxane 16 (76% yield). The iodo-substituted rotaxane 15 isolated as a remarkably stable byproduct offers a new synthetic potential demonstrated by the preparation of 16.
Embryotoxicity studies of tri-n-butyltin(IV) complexes of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid and 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1…
2005
The toxicity studies of free 5-[(E)-2-(aryl)-1-diazenyll-2-hydroxybenzoic acid and 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyllbenzoic acid and their tri-n-butyltin(IV) complexes were evaluated by using sea urchin early developmental stages as recommended model organisms for toxicity tests. The novel complexes, as the parent tri-n-butyltin(IV) chloride (TBTCl), caused mitosis block and induced high embryonic mortality in sea urchin. Copyright (c) 2005 John Wiley & Sons, Ltd.
H2-Antihistaminika, 33. Mitt. Synthese und H2-antagonistische Aktivität heteroaromatischer (Thio)Carboxamide und Triazol(thi)on-Derivate des Piperidi…
1987
Die Zyklisierung der (Thio)Semicarbazide la, b mit N-Cyan-diphenylimidocarbonat, N-Cyan-dimethyldithioimidocarbonat, Aminocrotonsaurenitril und Acetessigester gibt die heteroaromatischen (Thio)Carboxamide 5a, b und 7–9. Beim Einwirken von NaOH auf die (Thio)Biharnstoffe 12 und 13 sowie die (Oxa)Thiadiazoldiamine 19 und 20 werden die Triazol(thi)one 15 und 17 erhalten. Am Vorhof des Meerschweinchens zeigen 5a, 7 und 8 eine mit Cimetidin vergleichbare Histamin-H2-antagonistische Wirkung. H2-Antihistaminics, XXXIII: Synthesis and H2-Antagonistic Activity of Heteroaromatic (Thio)Carboxamides and Triazole(thi)one-Derivatives of Piperidinomethylphenoxypropylamine The (thio)semicarbazides la, b ar…
ChemInform Abstract: Epoxidation of Olefins with a Silica-Supported Peracid.
2012
Anhydrous [2-percarboxyethyl] functionalized silica (2a) is an advantageous oxidant for performing the epoxidation of olefins 1. Epoxides 3 do not undergo the ring-opening reactions catalyzed by the acidic silica surface, except for particularly activated cases such as styrene oxide. The hydrophilic and acidic character of the silica surface does not interfere with the directing effects exerted by allylic H-bond acceptor substituents. The alkenes 1 carrying hydroxyl groups react with silica-supported peracid 2a faster than unsubstituted alkenes, thus reversing the trend known for reactions with soluble peracids. These results are attributed to the H-bond interactions of substrate 1 with the…
Behavior of carbohydrate-based material in black liquor during heating
2004
One industrial softwood Kraft black liquor was heat-treated (at 175 ?C and 190 ?C for 15-60 min) together with laboratory-made soda-AQ (wheat straw and reed canary grass) and Kraft (reed canary grass) black liquors (at 190 ?C for 30 min). The feedstock black liquors were characterized with respect to their polysaccharide (mainly xylem) and aliphatic carboxylic acid contents before and after the heat treatments. It was noted that, due to the higher amount of polysaccharides in the non-wood black liquors (8.2-16.6% of d.s) compared to that in the softwood black liquor (1.4% of d.s), the heat treatment in the former case resulted in a 5-30% increase in the amount of aliphatic acids formed by v…