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61.
Alexander D Dilman Pavel A Belyakov Vladimir A Tartakovsky 《Tetrahedron letters》2004,45(19):3741-3744
Silyl enol ethers bearing three pentafluorophenyl groups at the silicon atom are described. These compounds undergo uncatalyzed aldol reactions with aliphatic, α,β-unsaturated, and aromatic aldehydes. The observed reactivity is analyzed in terms of the Lewis acidity of the silyl fragment. 相似文献
62.
Genosar L Lasitza T Gepshtein R Leiderman P Koifman N Huppert D 《The journal of physical chemistry. A》2005,109(21):4852-4861
The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2. 相似文献
63.
Klára Melánová Ludvík Beneš Vítězslav Zima Jan Svoboda Miroslava Trchová Jiří Dybal 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):95-101
Intercalation compounds of α-Zr(HPO4)2 · H2O with 1,2-alkanediols (from C3 to C16) have been prepared by replacing 1-propanol in α-Zr(HPO4)2 · 2C3H7OH with the desired 1,2-alkanediols by a treatment in a microwave field. It was found that the intercalates contain 1.5 molecules
of diol per formula unit. The diol molecules are placed between the host layers in a bimolecular way with their aliphatic
chains tilted at an angle of 51°. The diol molecules are anchored in the interlayer space by H-bonds. A mixed intercalate,
containing 1,2-butanediol and 1,2-decanediol in a roughly equimolar ratio, is formed when the α-Zr(HPO4)2 · 2C3H7OH intercalate, suspended in a mixture of 1,2-butanediol and 1,2-decanediol, is exposed to microwave radiation. No new phase
containing both types of the guest molecules was observed when the 1-propanol intercalate, suspended in a mixture of 1-propanol
and 1,2-octanediol, is exposed to microwave radiation. 相似文献
64.
Zusammenfassung An praktischen Beispielen wurde gezeigt, in welcher Weise die Trennung organischer Verbindungen mittels Papierchromatographie erzielt werden kann. Man ist nicht auf einige bewährte Lösungsmittel systeme allein angewiesen, sondern kann von Fall zu Fall systematisch neue und geeignete Systeme benützen. Es hat sich bewährt, sich nach den elementaren Löslichkeitsregeln für organische Stoffe zu richten, unter der Voraussetzung, daß die zu chromatographierende Verbindung in der stationären Phase gut, in der mobilen Phase dagegen weniger löslich ist. Durch Änderung der stationären Phase (Wasser, nicht wäßriges, polares Lösungsmittel, nicht polares Lösungsmittel) oder der Polarität und Zusammensetzung der mobilen Phase kann man das Wandern der Flecke am Chromatogramm beeinflussen, beliebige RfWerte erhalten und in vielen Fällen auch eine beliebige Reihenfolge der Verbindungen am Chromatogramm erzielen.Da die Löslichkeit organischer Verbindungen von intermolekularen Kräften abhängig ist, erscheint das Problem im Zusammenhang mit strukturellen Einflüssen sehr kompliziert und muß für jeden Fall auf eigene Weise gelöst werden. Die Löslichkeitseigenschaften können weiter durch Benutzung reaktiver Lösungsmittel beeinflußt werden, die z. B. die Verbindungen in wasserlösliche Salze überführen können. Dabei ist an die möglichen Komplikationen, die bei ionisierbaren Verbindungen durch Dissoziation und Hydrolyse entstehen können, zu achten.Von den Hauptfaktoren, die eine Trennung ermöglichen können, seien die folgenden erwähnt: funktionelle Gruppen, ihre Anzahl, Polarität, gegenseitige Stellung, bzw. ihre Basizität oder Azidität, C-Atomanzahl in homologen Verbindungen, inter- und intramolekulare Wasserstoffbindungen, sterische Faktoren u. a. Es ist dann von der Art des gewählten Lösungsmittelsystems abhängig, welche der genannten Faktoren im Vordergrund stehen und welche beseitigt werden.Wenn die Löslichkeitsunterschiede der zu trennenden Stoffe zu gering sind, um gute Trennungen zu ermöglichen, ist es zweckmäßig, die Verbindungen in solche Derivate zu überführen, deren Strukturunterschiede größer sind.
Summary Practical examples are given to show how organic compounds can be separated by means of paper chromatography. The operator is not limited to tested solvent systems, but can use new suitable systems as the occasion demands. It has been found best to abide by the elementary rules of solubility of organic compounds, provided the compound to be chromatographed is quite soluble in the stationary phase but less soluble in the mobile phase. By altering the stationary phase (water, nonaqueous, polar solvent, non-polar solvent) or the polarity and composition of the mobile phase, the migration of the stains in the chromatogram can be influenced, selectedR f -values can be obtained, and in many cases it is also possible to secure a desired succession of the compounds on the chromatogram.Since the solubility of organic compounds depends on intermolecular forces, the problem in connection with structural influences appears very complicated and must be solved individually for each case. Moreover, the solubility characteristics can be affected by using reactive solvents; for instance, the compounds can be converted into water soluble salts. Under such circumstances, sight must not be lost of the complications which may arise because of the dissociation and hydrolysis of ionizable compounds. The following are among the chief factors, which may make a separation possible: functional groups, their number, polarity, relative position, their basicity or acidity, C-atom number in homologous compounds, inter- and intramolecular hydrogen bonds, steric factors, etc. It then depends on the type of solvent system selected, which of these factors are predominant and which can be neglected or eliminated.If the solubility differences are too slight to permit good separations, the compounds to be separated should, if possible, be converted into derivatives whose structural differences are more pronounced.
Résumé Des exemples pratiques montrent comment il est possible d'effectuer la séparation de combinaisons organiques par Chromatographie sur papier. Il n'est pas uniquement fait appel à des systèmes de solvants éprouvés mais, dans certains cas, de nouveaux systèmes appropriés sont systématiquement utilisés.Il s'est avéré satisfaisant de faire appel aux règles élémentaires de solubilité des substances organiques sous réserve que la combinaison à chromatographier soit suffisamment soluble dans la phase stationnaire et moins soluble dans la phase mobile. En faisant varier la phase stationnaire (eau, solvant non aqueux, solvant polaire, solvant non polaire) ou la polarité et la composition de la phase mobile, il est possible d'influencer la migration des taches du chromatogramme, d'obtenir des valeurs deR f désirées et, dans de nombreux cas, d'obtenir les combinaisons dans un ordre déterminé sur le chromatogramme.La solubilité des combinaisons organiques étant fonction des forces intermoléculaires il en résulte que le problème se complique considérablement dans la mesure où l'on considère les influences structurelles et que chaque cas particulier doit recevoir une solution qui lui est propre. Les propriétés de solubilité peuvent en outre être influencées par l'emploi de solvants réactifs qui peuvent transformer, par exemple les combinaisons en sels solubles dans l'eau. Il faut alors tenir compte des possibilités de complications qui peuvent apparaître par dissociation et hydrolyse des combinaisons ionisables.Parmi les principaux facteurs qui permettent une séparation, il convient de mentionner les suivants: les groupes fonctionnels, leur nombre, leur polarité, leur position relative, ou encore leur acidité ou leur basicité, le nombre d'atomes de carbone de combinaisons homologues, les liaisons hydrogène inter- et intramoléculaires, les facteurs stériques, etc. Suivant la nature du système solvant choisi pourront alors varier les facteurs dont l'effet est prépondérant et ceux dont l'effet est nul. Lorsque les différences de solubilité des substances à séparer sont trop faibles pour permettre des séparations satisfaisantes, il est commode de transformer les combinaisons en dérivés dont les différences de structure soient plus importantes.相似文献
65.
The halothane???acetone and fluoroform???acetone complexes are studied using the second‐order Møller–Plesset (MP2) method with a cc‐pVTZ basis set and the density functional theory (DFT) method with a TZVP basis set. Whereas halothane exhibits a small red shift upon complexation, fluoroform shows a pronounced blue shift. To explain this difference in behavior, we perform symmetry‐adapted perturbation theory (SAPT) and natural bond orbital (NBO) analyses. Although the composition of the total stabilization energy of each complex is different, that alone does not provide a satisfactory explanation for the difference in the spectral shifts. This difference is interpreted as a result of the interplay of the hyperconjugation and rehybridization mechanisms. The small and surprising red shift of the C? H stretching frequency of halothane, which resulted from the complexation of this species with acetone,is explained by the compensation of the two above‐mentioned mechanisms. On the other hand, the fluoroform???acetone complex exhibits a blue shift of the C? H stretching frequency upon complexation, the most likely reason for this shift being a concerted occurrence of the hyperconjugation and rehybridization mechanisms. The calculated shift of the C? H stretching vibration frequencies of halothane (+27 cm?1) agree with the experimental value of +5 cm?1. 相似文献
66.
67.
Double gradient ion chromatography on a short carboxybetaine coated monolithic anion exchanger 总被引:1,自引:0,他引:1
An ultra-short 1.0 x 0.46 cm carboxybetaine coated monolithic anion exchanger has been used with a new double gradient ion chromatography (DG-IC) technique. The novel monolithic column can be used with flow rate gradients giving excellent peak efficiencies, and retention times can be simultaneously reduced through combining flow gradients with an eluent pH gradient. 相似文献
68.
Six new dinuclear or trinuclear FeIII complexes involving tetradentate Schiff bases N,N′-bis(salicylidene)ethylenediamine
(salenH2) or bis(salicylidene)-o-phenylenediamine (salophH2) with 2,5-pyridinedicarboxylic acid, acetylenedicarboxylic acid
or 1,3,5-benzenetricarboxylic acid have been synthesized and characterized by means of elemental analysis, i.r. spectroscopy,
thermal analyses, conductivity measurements and variable-temperature magnetochemical measurements to the temperature of liquid
nitrogen. The complexes can be characterized as high-spin distorted octahedral FeIII bridged by carboxylic acids. The dicarboxylic
or tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange. The antiferromagnetic coupling
parameters J vary in the -1.99 to -5.47cm-1 range for the dimers, whilst the values are -2.35 and -1.42cm-1 for the salen
and saloph trimers, respectively. One complex, namely [{Fe(saloph)}2(2,5-dicarpy)]middot H2O, obeys the Curie-Weiss law.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
69.
Summary A flow-through two electrode wall-jet cell with a platinum measuring electrode and a cell volume of 20 nl has been designed and evaluated. It has been used to detect phenols by reversed phase liquid chromatography using short micro bore columns. The linear dynamic range between the measured current and the concentration is greater than 103 (1.5×10–7–5×10–4 mol/l) and the minimum analyzable amount was found to be 10 pg for pyrocatechol. A negligible broadening in the detector permits the use of micro columns down to 0.5 mm internal diameter, packed with 5 m particles, without any substantial distortion of eluted zones.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献
70.
Accumulation of five heavy metal ions by five species of wood-rotting basidiomycetes during a 9-day cultivation was studied. Contents of Cd, Cu, Pb, and Zn were measured using ICP-MS; the amount of mercury was determined directly in solid samples using the Advanced Mercury Analyser. A standard operation procedure for the sample preparation and determination of metal content was developed and validated. Presence of Cd, Cu, Hg, and Pb decreased the accumulation of zinc by the fungi. The basidiomycete Pycnoporus cinnabarinus exhibited the highest metal binding capacity of all fungi tested. 相似文献