Supramolecular Polymers Formed by Modified Cyclodextrins

6-Hydrocinnamoyl -cyclodextrin(6-HyCiO--CD), 6-hydrocinnamoyl -cyclodextrin(6-HyCiO--CD), 6-cinnamoyl -cyclodextrin(6-CiO--CD), and 6-cinnamoyl -cyclodextrin (6-HyCiO--CD) have been prepared.6-HyCiO--CD formed an intramolecular complex in an aqueous solution. 6-HyCiO--CD formed weak intermolecular complexes.6-CiO--CD formed intermolecular complexes to give supramolecular oligomers. 6-CiO--CD formed insoluble supramolecular complexes in the solid state. The structures of these complexes are discussed.     

Formation of Supramolecular Polymers Constructed by Cyclodextrins with Cinnamamide

-Cyclodextrin having cinnamamide at 6- or 3-positions (6-CiNH--CD, 3-CiNH--CD) and -cyclodextrin with cinnamamide on 6-position (6-CiNH--CD) have been prepared. Supramolecular structures were formed in the solid state or aqueous solutions and characterized by measurements of NMR and vapor pressure osmometry (VPO). The results indicate that 6-CiNH--CD formed insoluble supramolecular polymers in the solid state, while 6-CiNH--CD and 3-CiNH--CD formed supramolecular complexes in aqueous solutions. 6-CiNH--CD was found to form a dimer in an aqueous solution. 3-CiNH--CD formed intermolecular complexes to give supramolecular polymers. The differences of the position of guest part on cyclodextrins caused to give a variety of supramolecular structures in aqueous solutions.     

Thermal desorption analysis:

Experiments on water desorption from silicate glass powders of different chemical compositions were carried out by means of DSC. In order to establish the desorption energy distributions, a model of the heterogeneous surface was applied to the thermoanalytical desorption curves, and the results are discussed together with contact angle measurements on flat polished glass samples.The maxima in the desorption curves shift to lower temperature with increasing hydrophobic character; this is caused by divalent cations such as Pb²⁺, Ca²⁺ and Zn²⁺, while alkali metal ions are responsible for an increase in the hydrophilic behaviour.

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Zusammenfassung Wasserdesorptionsexperimente an Silikatglaspulvern unterschiedlicher Zusammensetzung wurden mittels DSC ausgeführt. Für die Berechnung von Desorptionsenergieverteilungen wurde ein Modell der heterogenen Oberfläche genutzt und zusammen mit Randwinkelmessungen an glatten, polierten Glasoberflächen diskutiert. Das Maximum der Desorptionskurven verschiebt sich mit wachsendem hydrophoben Verhalten nach tieferen Temperaturen, wofür divalente Kationen wie Pb²⁺ Ca²⁺ Zn²⁺ verantwortlich sind, während Alkaliionen das hydrophile Verhalten begünstigen.

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. . , , , .

     

Effect of Rh/Al2O3 on the reduction of ZnO in a mechanical mixture of these components

The effect of reoxidation temperature on TPR of 5% Rh/Al₂O₃ catalyst and its mechanical mixture with ZnO has been investigated. The results suggest bimodal character of supported rhodium and surprisingly high effect of this metal on ZnO reduction in the mixture.

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5% Rh/Al₂O₃ ZnO. , ZnO .

     

Thermische Zersetzung der [Pd(NH3)4]-Form von Mordenit

Zusammenfassung Die Zersetzung der Palladium-tetrammin-Form von Mordenit in inerter und oxdlativer Atmosphäre wird mittels TG, DTA und automatischer Titration des freigesetzten Ammoniaks untersucht. In N₂-Atmosphäre erfolgt bei 590 K eine Redoxreaktion under Bildung von Pd und NH₄-Mordenit als feste Reaktionsprodukte. Bei höheren Temperaturen erfolgt dann die bekannte Deammonisierung und Dehydroxylierung des NH₄-Mordenits.In O₂-Atmosphäre entstehenzum Teil über wasser- bzw. hydroxylgruppenhaltige Intermediäre—PdO und H-Mordenit als feste Reaktionsprodukte, die unter H₂O-Bildung zu Pd-Mordenit weiterreagieren. Beim Gitterzusammenbruch (1130–1210 K) entsteht metallisches Pd und eine äquivalente Menge an Sauerstoff.

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The decomposition of [Pd(NH₃)]₄-mordenite in inert and oxidizing atmospheres was studied by TG/DTA and titration of the evolved ammonia. In nitrogen, a redox reaction proceeds at 600 K, resulting in Pd- and NH₄-mordenite as solid reaction products. At higher temperatures, the usual deammonization and dehydroxylation of NH₄-mordenite take place. In oxygen, PdO and H-mordenite are formed as solid reaction products, partly via intermediates containing hydroxyl groups and water. PdO is involved in the dehydroxylation of H-mordenite at higher temperatures, which results in the formation of the Pd-form and water. Lattice collapse at 1130–1210 K involves the formation of metallic Pd and the evolution of an equivalent amount of oxygen.

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, [d(N₃)]₄- . - 600 -. . , , . - - . 1130–1210 .

     

Free radical properties of the magnesium oxide surface, I

Free radical properties of MgO catalysts obtained by thermal decomposition of Mg(OH)₂ in nitrogen, hydrogen and oxygen have been investigated. All the oxides show one-electron donor properties (reduction of adsorbed tetracyanoethylene and trinitrobenzene). Only the MgO calcined in oxygen shows one-electron acceptor properties (oxidation of adsorbed perylene). Acetaldehyde transformations were studied on the above catalysts. The MgO calcined in oxygen appeared to be the most active. Presumably, its activity is due to one-electron acceptor centers on the surface.

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- MgO, Mg(OH)₂ , . ( ). MgO, , ( ). . MgO. . , .

     

Thermal and X-ray analysis studies of UO3 gel microspheres

The thermal decomposition behaviour of UO₃ gel microspheres has been studied. Thermal analysis involved DTA, TG, DTG and X-ray examination. The effects of washing the UO₃ gel microspheres with hot water and with ammonia solution were investigated, as were the effects of soaking the microspheres in ammonia solution before or after washing on the crystallite size. The results indicate that the thermal decomposition of UO₃ gel microspheres includes five steps: the first two for dehydration, the third for ammonia removal, the fourth for ammonia oxidation and the last step for UO₃ recrystallization.

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Zusammenfassung Die thermische Zersetzung von UO₃-Gelmikrokugeln wurde mittels DTA, TG, DTG und Röntgendiffraktometrie untersucht. Die Auswirkungen des Waschens der UO₃-Gelmikrokugeln mit heißem Wasser und mit Ammoniaklösungen sowie der Einfluß des Wässerns der Mikrokugeln vor und nach dem Waschen mit Ammoniaklösungen auf die Kristallitgröße wurden untersucht. Die thermische Zersetzung der UO₃-Gelmikrokugeln verläuft in 5 Schritten: in den ersten beiden erfolgt die Dehydratisierung, im dritten die Abgabe und im vierten die Oxydation von Ammoniak und schließlich im letzten Schritt die Rekristallisation von UO₃.

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, , ₃. , . , ₃ , , — , — , ₃.

     

Inclusion Complexes of Cyclodextrins with 4-Amino-1,8-Naphthalimides

The formation of inclusion complexes between 4-amino-1,8-naphthalimides and cyclodextrins (CDs) was investigated. The naphthalimides used in the study were 4-amino-1,8-naphthalimide (I) and4-(2-phosphonoethylamino)-N-(2-phosphonoethyl)-1,8-naphthalimide,tetraethylester (II). The CDs employed were -CD, -CD, -CD, HP--CD, HP--CD andHP--CD (HP = hydroxypropyl). Evidence for complex formation was obtained from the changes in the fluorescence spectra of the dyes in the presence of increasing amounts of the CDs. The most striking changes were observed with HP--CD and HP--CD. Treatment of the data using Benesi–Hildebrand plotswas consistent with a 1:1 inclusion model. The determined stabilityconstants were (K_eq, M^-1): 106 (I:HP--CD, pH = 2.0), 193 (I:HP--CD, pH = 7.0), 113 (I:HP--CD, pH = 7.0), 155(II:HP--CD, pH = 2.0), 121 (II:HP--CD,pH = 7.0), 301 (II:HP--CD, pH = 7.0). It can beconcluded that compound I forms a more stable complex with HP--CD than with HP--CD. Compound II, on the other hand, forms a more stable complex with HP--CD than with HP--CD.     

The oxonium theory in the light of an optical study of the hydrogen bond in some monovinyl ethers of glycols and polyglycols

Summary An optical investigation of some monovinyl ethers of glycols and polyglycols has indicated the presence of intermolecular hydrogen bonds in the liquid state, and this is confirmed by data derived from other phycicochemical investigations. The presence of an intermolecular hydrogen bond explains the anomalous valency of the oxygen atom of the investigated class of ethers (Its oxonium character), and also peculiarities of the properties of these ethers.     

Reaction of 1,5-dikitones

1,3-Diphenyl-1-(,-dimethyltetrahydro--pyron--yl)-2-dimethylaminomethyl-3-propanone was obtained by Mannich condensation of 1,3-diphenyl-1-(,-dimethyltetrahydro--pyron-yl)-3-propanone with formaldehyde and dimethylamine hydrochloride. Its deaminomethylation, deamination, and conversion to the corresponding oxatetrahydroquinoline on reaction with hydroxylamine hydrochloride were studied.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 738–740, June, 1973.     

Complexation of 6-Deoxy-6-(aminoethyl)amino-β-cyclodextrin with Sodium Cholate and Sodium Deoxycholate

In order to study its guest binding and the inclusion phenomena, 6-deoxy-6-(aminoethyl)amino--cyclodextrin (CDN) was synthesised and its binding properties examined. The complexation phenomena of sodium cholate (NaC) and sodium deoxycholate (NaDC) with CDN has been monitored by the NMR method using ¹³C chemical shift data. The method of continuous variation Job's method has been used to determine the stoichiometry of these supramolecular complexes. The Job's plot confirms the 1 : 1 supramolecular complex for NaC: CDN and the 1 : 2 supramolecular complex for NaDC: CDN. The interaction of NaC and NaDC with CDN has been obtained through two-dimensional Rotational Nuclear Overhauser Effect Spectroscopy (ROESY) NMR. Equilibrium constants were also obtained from ¹³C chemical shift data (C-1, C-3 & C-4) at different pH values (7, 9, & 11).     

Application de la thermogravimetrie,de l'analyse thermique differentielle et de la spectrographie d'absorption infrarouge a l'etude de la reaction entre l'oxyde de chrome-III et les nitrates alcalins,I

Résumé On a étudié la réaction à l'état solide et fondu entre l'oxyde de chrome trivalent et les nitrates alcalins par analyse thermogravimétrique et analyse thermique différentielle. Les conditions optimales pour l'oxydation complète du chrome(III) en chrome(VI) ont été déterminées. De plus, on a établi le rendement de la réaction. La spectrophotométrie d'absorption infrarouge a permis d'identifier les phases formées aux divers stades de la réaction.

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The reaction between trivalent chromium and alkali nitrates in the solid and molten phase was studied by thermogravimetry and differential thermal analysis. The optimum conditions for the oxidation Cr(III) Cr(IV) as well as the yield were determined. The phases existing at various reaction stages were identified by infrared spectroscopy.

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Zusammenfassung Die Reaktion in fester sowie in geschmolzener Phase zwischen dreiwertigem Chrom und Alkalinitraten wurde thermogravimetrisch und differential-thermoanalytisch geprüft. Die optimalen Umstände der Oxydation Cr(III) Cr(VI) sowie die Reaktionsausbeute wurden bestimmt. Durch infrarote Spektroskopie wurden die in verschiedenen Reaktionszeitpunkten vorliegenden Phasen identifiziert.

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() () . Cr(III) Cr(IV) . .

     

Thermogravimetric and kinetic study of a clodronic acid complex formed with sodium

Thermal stability of the clodronic acid complex formed with sodium (Na₂CCl₂(HPO₃)₂ ·4H₂O) was studied using both dynamic and isothermal thermogravimetric analyses as well as mass spectra. The thermal decomposition has two stages: dehydration and loss of two molecules of hydrogen chloride. Using the isothermal TG data the first step was found to be a phase-boundary reaction while the second step obviously cannot be described with just one reaction mechanism. The final residue of the dynamic TG analyses above 810 K was found to be sodium metaphosphate.

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Zusammenfassung Sowohl mittels dynamischer und thermogravimetrischer Untersuchungen als auch and Hand von Massenspektren wurde die thermische Stabilität des mit Natrium gebildeten Säurekomplexes Na₂CCl₂(HPO₃)₂·4H₂O untersucht. Die thermische Zersetzung vollzieht sich in zwei Schritten: Dehydratation und Verlust von zwei Molekülen HCl. Auf Grund der isothermen TG Angaben ist der erste Schritt eine Phasengrenzreaktion, während der zweite Schritt mit einem einzigen Reaktionsmechanismus nicht eindeutig beschrieben werden kann. Das Endprodukt der DTG Analyse oberhalb 810 K erwies sich als Natriummethaphosphat.

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-Na₂CCl₂/HPO_3/2·4H₂O — , - . , , , . , , . 810 .

     

Inter-ring η6⇌η5 haptotropic rearrangements of 18ē and 19ē (η5-pentamethylcyclopentadienyl)(η6-9-methylfluorenyl)iron complexes

New cationic complexes [(⁶-C₁₃H₁₀)Fe(⁵-Cp^*)]PF₆ and [(⁶-9-CH₃-C₁₃H₉)Fe(⁵-Cp^*)]PF₆ were obtained by the reaction of Cp^*Fe(CO)₂Br with fluorene and 9-methylfluorene, respectively. Deprotonation of these complexes byt-BuOK in THF affords zwitter-ionic compounds (⁶-C₁₃H₉)Fe(⁵-Cp^*) and (⁶-9-CH₃-C₁₃H₈)Fe(⁵-Cp^*) (A). WhenA is heated in nonane at 150 °C it undergoes ⁶⁵ inter-ring rearrangement with the formation of hexamethyldibenzoferrocene (B). The electrochemical behavior ofA andB was studied by cyclic voltammetry. One-electron reduction ofA andB to the corresponding radical anions induces inter-ring haptotropic rearrangementA ^.–B ^.–. The equilibrium in the 19 state is shifted to the ⁶-isomeric radical anionA ^.–, while in the 18 precursors, it shifts to the ⁵-isomerB.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319–324, February, 1994.The authors are grateful to D. V. Zagorevskii (A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) for recording and interpreting the mass spectra, and to A. A. Borisenko (Moscow State University) for recording the NMR spectra.This work was financially supported by the Russian Foundation for Basic Research (Grant 93-03-5209).     

Spectral and thermal studies of copper(II) complexes of 3- and 4-pyridinealdoxime

Copper(II) complexes of 3- and 4-pyridinealdoxime have been prepared and analyzed by spectroscopic (ir and diffuse reflectance) and thermoanalytical (TG, DTG and DTA) techniques. For both these systems, only species with metal: organic ligand: chloride ratio of 122 were found, and the organic ligand appears as a neutral molecule. The spectral data suggest a polymeric structure where the copper(II) ions are in a distorted octahedral environment.The thermal decompositions occur through the reduction of copper(II) to copper(I) and the conversion of the residual organic ligand into acid amide, as found for dihydrogenbis(pyridine-2-aldoxime) copper(II) chloride, but the initial decomposition temperatures are slightly increased, giving rise to the thermal stability sequence:

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Zusammenfassung Kupfer(II)-Komplexe von 3- und 4-Pyridinaldoxim wurden hergestellt und spektroskopisch (IR und diffuse Reflexion) sowie thermoanalytisch (TG, DTG und DTA) analysiert. Für beide Systeme wurden nur Species mit einem Metall:Ligand:Chlorid-Verhältnis von 122 gefunden. Der organische Ligand liegt als neutrales Molekül vor. Die Spektren deuten auf eine polymère Struktur hin, in der die Kupfer(II)-Ionen in einer verzerrten oktaedrischen Koordination vorliegen. Die thermischen Zersetzungen verlaufen über die Reduktion von Cu(II) zu Cu(I) und die Umwandlung des verbleibenden organischen Liganden in Säureamid, wie für Dihydrogen-bis(pyridin-2-aldoxim)-kupfer(II)-chlorid gefunden wurde, aber die Temperaturen des Beginns der Zersetzung und damit die thermische Stabilität steigen in der Reihenfolge [Cu(Py₄-CHNOH)₂Cl₂][Cu(Py₃-CHNOH)₂Cl₂]>[Cu(Py₂-CHNOH)₂]Cl₂ etwas an.

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(, ) ( ) 3- 4- . 122, . , . -( -2-)- . , , , : Cu(4-Py-CHNOH)₂Cl₂Cu(3-Py-CHNOH)₂Cl₂>Cu(2-Py-CHNOH)₂Cl₂.

     

Crystal Structure of Dehydrated Wairakite

Singlecrystal Xray analysis was employed to study dehydrated wairakite Ca_0.97Na_0.06K_0.03×[Al_1.95Si_4.04O₁₂] with the following parameters: a = 18.260(4) , b = 18.284(4) , c = 13.432(3) , = 90.28(3)°, V = 4989(3) ³, Z = 16, space group B2₁/d. A comparison was carried out with the structure of the hightemperature (600°) phase, space group I4₁/acd. The coordination of the Ca cations increased from 4 to 4 + 1. Additional ligands were acquired from the fourmember ring of the framework upon its deformation and a pairwise countershift of the cations along the c axis. This resulted in a pseudotetragonal unit cell with a doubled volume and lowered symmetry.     

Kinetic simulation of oxidative dehydrogenation of n-butenes over SnO2?Sb2O4 catalysts

A previously suggested reaction mechanism was utilized to evaluate a kinetic model for the oxidation of n-butenes over ShSb=31 mixed oxide catalyst. With this model, kinetic curves measured at 673 K were simulated, illustrating the changes of amounts of undetectable surface components, too.

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- SnSb=31 . , 673 K, .

     

Heterobinuclear and heterotrinuclear transition-metal μ-allenyl complexes

Binuclear and trinuclear transition-metal -allenyl complexes—especially mixedmetal complexes—are reviewed. In recent years, a number of such compounds have been prepared by use of several synthetic methods. The most general of these methods, viz. reactions of metal propargyls and of the lower nuclearity metal allenyls with low-valent metal complexes such as metal carbonyls and platinum(0) compounds, are considered in some detail. The structures of the binuclear metal -¹,²- and -³,²-allenyl complexes and of the trinuclear metal ₃-¹,²,²-allenyl complexes—both triangular and open—are presented and compared. Trends in the¹H and¹³C NMR spectroscopic properties of these compounds are examined. Some aspects of reaction chemistry of the heteronuclear platinum-ruthenium -¹,²-allenyl complexes are presented.