Molecular encapsulation of transition metal complexes in cyclodextrins. Part 2. Synthesis and crystal structures of 2:1 adducts between α-cyclodextrin and metallocenium hexafluorophosphates [η5-C5H5)2M]PF6(M = Fe,Co, Rh)

The title metallocenium salts form crystalline 2:1 host:guest inclusion compounds with-cyclodextrin, [(⁵-C₅H₅)₂M]PF₆ · 2-CD · 8H₂O (1, M = Fe;2, M = Co;3, M = Rh). The X-ray crystal structures of1 and3, and the lattice constants, crystal system and space group of2 have been determined. Crystal data: triclinic, space groupP1 (No. 1),Z = 1;1,a = 13.865 (2) Å,b = 13.839 (2) Å,c = 15.520 (2) Å, = 91.43 (2)°, = 85.81 (2)°, = 120.22 (2)°, andR _F = 0.089 for 4257 observed MoK reflections [I > 3(I)];2,a = 13.810 (2) Å,b = 13.872 (2) Å,c = 15.560 (2) Å, = 93.99 (2)°, = 87.06 (2)°, = 120.04 (2)°;3,a = 13.756 (1) Å,b = 13.863 (1) Å,c = 15.561 (2) Å, =94.39 (1)°, = 86.92 (1)°, = 119.89 (1)°, andR _F = 0.061 for 11142 observed MoK reflections [I > 3(I)]. In the crystals of1 and3, two -cyclodextrin molecules are arranged head-to-head to form a dimer by means of intermolecular hydrogen bonding across the secondary hydroxyl faces of adjacent -CD monomers. The dimers are stacked along the crystallographicc axis to form a channel-type structure. The metallocenium cation is encapsulated within the cavity of the dimer, while the PF ₆ ^– anion is located outside the cavity, being centered between the primary hydroxyl faces of adjacent dimers. Eight water molecules of hydration per asymmetric unit reside in the spaces between the -CD columns. In view of the almost identical crystal data for2 a similar structure can be assumed for the cobaltocenium adduct.     

The structures of macrocyclic heterocyclophane inclusion complexes

Crystal and molecular structures of (1:1) molecular complexes of N,N,N,N-tetramethyl-2, 11, 20, 29-tetraaza [3.3.3.3] paracyclophane (1) with CHCl₃, CH₂Cl₂, CH₃CN and CO₂ are reported. The macrocycle has square-box structure, giving hydrophobic cavity surrounded by four benzene rings. The guest molecules are included in the cavity. The uncomplexed1 was found to have a rectangular form, indicating large conformational flexibility of1. In solution,1 is achiral because rapid RS interconversion, but in solid, the macrocyclic conformation is frozen as R-conformer or S-conformer. The macrocycles with the same chirality are stacked alongb-axis to form chiral molecular columns, R-colums or S-columns. Complexes of1 crystallize differently depending on the guest molecules. R-columns (S-columns) packed alonga-axis produce R-layers (S-layers), which are further packed alongc-axis using R-layer to R-layer contact (RR) or SS and RS or SR. The crystals of1·CHCl₃ are formulated as--RRR--=[R]_n (Type I, chiral) and those of1·CH₃CN or1·CO₂ and1·CH₂Cl₂ are represented by [RS]_n (Type IIA, racemic) and [RRSS]_n (Type IIB, racemic), respectively.     

Kinetic study of the thermal dehydration of syngenite K2Ca(SO4)2·H2O under non-isothermal conditions

Different calculation methods applied to TG, DTG and DTA curves obtained with a Mettler Thermoanalyzer at one or several heating rates have been tested. It has been shown that the dehydration of syngenite can best be described by the Avrami equation I [–1n(1–)]^1/2=3.46·10²¹exp (–2.73·10⁴/T)·t where is the degree of decomposition,T the absolute temperature, andt the time.The mean value of the activation energy is 54 kcal·mole^–1. This is in good agreement with the results obtained under isothermal conditions. The method of atava and kvára, supplemented by the numerical tables of Zsakó, is most useful in obtaining the kinetic equations describing the thermal decomposition of solids.

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Zusammenfassung Mit verschiedenen Berechnungsmethoden wurde anhand der TG, DTG und DTA-Kurven, die bei einer und mehreren Aufheizgeschwindigkeiten der Probe im Thermoanalysator der Firma Mettler erhalten wurden bewiesen, daß die kinetische Gleichung zur Beschreibung des Dhydratisierungsprozesses des Syngenits folgende Gestalt hat: [–1n(1–)]^1/2=3.46·10²¹ exp (–2.73·10⁴/T)·t (-Zersetzungsgrad,T absolute Temperatur,t-Zeit) Der Mittelwert der Aktivierungsenergie beträgt: 54 kcal·mol^–1. Die Gleichung und die Werte der kinetischen Parameter stimmen gut mit den Ergebnissen der isothermen Experimente überein. Bei den Untersuchungen thermischer Reaktionen der Zersetzung von Festkörpern hat sich die Methode von atava und kvára, ergänzt durch die numerische Tabelle von Zsakó als besonders geeignet erwiesen.

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Résumé Divers procédés de calcul appliqués aux courbes TG, TGD et ATD obtenues à l'aide d'un thermoanalyseur Mettler, avec une ou plusieurs vitesses de chauffage, conduisent à l'équation cinétique suivante pour exprimer le processus de déshydratation de la syngénite: [–1n (1–)]^1/2=3.46·10²¹exp (–2.73·10⁴/T)·t où =degré de décomposition,T=température absolute,t=temps. La valeur moyenne de l'énergie d'activation est 54 kcal·mol^–1, en bon accord avec les résultats des études en conditions isothermes. La méthode de atava et kvára, combinée avec les tables numériques de Zsakó, s'est révélée la plus efficace pour l'obtention de l'équations décrivant la cinétique de la décomposition thermique des corps solides.

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« » -, , . , , : [–1n(1–)]^1/2=3.46·10²¹ exp (–2.73·10⁴/T)·t - ,— ,t — . , 54 . ^–1. , . , , -log() III III.

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The authors would like to thank Dr. E. M. Bulewicz of this Department for valuable discussions, and Dr. M. Szakowicz and Mr. B. Gawliczek for carrying out the measurements on the Mettler instrument at the Institute of Metallurgy at the School of Mining and Metallurgy in Cracow.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXVII. Alliosterol and allosides A and B from Allium suvorovii and Allium stipitatum — Structural analogs of furostanols

Two new glycosides of the cholestane series (allosides A and B) have been isolated from the fruit of the cocultivatedAllium suvorovii Rgi. andAllium stipitatum Rgl. (family Liliaceae, local name anzur). The acid hydrolysis of both compounds gave a sterol not previously described, which has been called alliosterol and has the structure of (22S)-cholest-5-ene-1, 3, 16, 22-tetraol, and the product of its dehvdration, which is (16S, 22S)-furost-5-ene-1, 3-diol. Alloside A is the 16-O--D-galactopyranoside, and alloside B the 16-O--D-galactopyranoside 1-O--D-glucopyranoside of alliosterol.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 231–241, March–April, 1991.     

Electronic spectrum and thermal decomposition of nickel(II) complex with bis(N-γ-pyridyl-4-phenylbenzamide-hydrazone)

The unit cell parameters and the space group of the investigated compound were determined by means of X-ray diffraction.Analysis of the diffusion-reflection spectra of the crystalline powder and the absorption spectra of its alcoholic solutions permitted identification and quantitative characterization of the absorption bands of the crystalline complex of NiL₂(ClO₄)₂·3H₂O.Application of differential-thermal analysis allowed determination of the mechanism of thermal decomposition of the compound. From these measurements, the expected configuration of the basic molecule was verified, involving determination of the number of non-coordinated water molecules.

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Zusammenfassung Mittels Röntgendiffraktionsmethoden wurden Gitterzellenkonstanten sowie die Raumgruppe der untersuchten Verbindung bestimmt. Durch Analyse der erhaltenen Diffusions-Reflexionsspektren von kristallinem Pulver und des Absorptionsspektrums einer alkoholischen Lösung der Verbindung war es möglich, die Absorptionsbanden des Kristallkomplexes NiL₂(ClO₄)₂·3H₂O zu identifizieren und quantitativ zu charakterisieren. Anwendung von Differentialthermoanalyse ermöglicht die Bestimmung des Mechanismus der Zersetzungsreaktion der Verbindung. Durch diese Messungen, einschliesslich der Bestimmung der Anzahl nichtkoordinierter Wassermoleküle, wurde die erwartete Konfiguration des Grundmoleküles überprüft.

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NiL₂(ClO₄)₂·₂, L-N-- -4- . L-N---4- . , , . . , .

     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXV. Structure of anzurogenin B from Allium suvorovii and Allium Stipitatum

A new genin of the spirostan series — anzurogenin B having the structure of 2,5-epoxy-(25R)-spirostan-3,6-diol — has been isolated form the collective fruit of the cocultivatedAllium suvorovii Rgl. andAllium stipitatum Rgl. (family Liliaceae).Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–221, March–April, 1988.     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .

     

Synthesis and structure of (pyridine) bis(acetylacetonato) (1-methyl-1-phenylethylperoxo) cobalt (III)

Synthesis and structure of (pyridine) bis(acetylacetonato) (1-methyl-1-phenylethylperoxo) cobalt(III) complex are described.

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() () (III).

     

Influence of the preparation method on the pore spectrum of Pt?Cr/Al2O3 and Pt?Sn/Al2O3 catalysts

It is shown that, in contrast to classical impregnation methods, in bimetallic catalyst production the texture of the carrier is stabilized by introducing the promoting ion on the surface of Pt/Al₂O₃ with vapors of CrO₂Cl₂ or SnCl₄. This is shown by a relatively slower decrease of the specific area and the volume of the pores upon calcination.

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, Pt/Al₂O₃- CrO₂Cl₂ SnCl₄ . .

     

An IR study of the Ziegler system Co(acad)3/Mg(n-butyl)2 in THF

Applying IR spectroscopy for studying the Ziegler system Co(acac)₃/Mg(Bu)₂ (Bu=n-butyl) in tetrahydrofuran, it could be shown that the following reactions take place: reduction of cobalt (III), exchange of the acetylacetonate groups and their interaction with Mg(Bu)₂.

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Co(acac)₃/Mg(Bu)₂ (Bu=-) - , (III), Mg(Bu)₂.

     

Quadrupole polarizability and hyperpolarizability of carbon monoxide

Summary We report a study of the electric dipole-quadrupole (A _,,), quadrupole-quadrupole (C _,,), dipole-octopole (E _,) polarizability and the dipole-dipole-quadrupole (B _,,) hyperpolarizability of carbon monoxide. All values are obtained from finite-field self-consistent field (SCF) and fourth-order manybody perturbation theory (MP4) calculations. Our best values for the dipole-octopole polarizability areE _z,zzz=60.19 andE _x,xxx=–38.06e ² a ₀ ⁴ E _h ^–1 . For the dipole-dipole-quadrupole hyperpolarizability we reportB _zz,zz=–296,B _xz,xz=–170,B _xx,zz=88 andB _xx,xx=–178e ³ a ₀ ⁴ E _h ^–2 .     

Triterpene glycosides of Hedera taurica. IV. Structure of hederosides A1, A2, D1, and D2 from the berries of Crimean ivy

New triterpene glycosides have been isolated from the berries of Crimean ivyHedera taurica Carr. (family Araliaceae) — hederoside A₁ (methyl ester of 3-O--D-glucopyranosylhederagenin) and hederoside D₁ 3-O-[O--D-glucopyranosyl]-(12)--D-glucopyranosyl]hederagenin and also the known glycosides 3-O--D-glucopyranosyloleanolic acid and 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranosyl]hederagenin. The structures of these compounds were established on the basis of the results of chemical methods and¹H and¹³C NMR spectroscopy.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 228–230, March–April, 1990.     

Triterpene glycosides of the holothurian Eupentacta pseudoquinquisemita

The holothurianEupentacta pseudoquinquisemita Deichmann collected in Kraternaya Bay, Ushishir Islands has yielded two triterpene pentaosides — the previously known cucumarioside C₂, and cucumarioside H, which is a new glycoside. With the aid of¹³C NMR spectroscopy and solvolytic desulfation its structure has been determined as 6-acetoxy-3-([3-O-methyl--D-xylopyranosyl-(1 3)--D-glucopyranosyl-(1 4)] [-D-xylopyranosyl-(1 4)] [-D-xylopyranosyl-(1 2)]--D-quinovopy-ranosyl-(1 2)-(4-O-sulfato--D-xylopyranosyloxy)holosta-7,22,24(trans)-triene. Cucumarioside H was also identified inEupentacta (=Cucumaria)fraudatrix from Posyet Bay, Sea of Japan.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 221–225, March–April, 1988.     

Glycosylation of triterpenoids of the dammarane series. VII. Dammar-24-ene-3α,12β,17α,20(S)-tetraol β-D-glucopyranosides

Glucosides have been synthesized from dammar-24-ene-3,12,17,20(S)-tetraol (betulafolienetetraol), isolated from the leaves ofBetula pendula. Condensation with -acetobromoglucose in the presence of silver oxide and silicate has given acetylated betulafolienetetraol 3- and 12- mono- and 3,12- and 3,20-di-O--D-glucopyranosides, the total yield of which amounted to 75–80%. The structures of the semisynthetic glycosides have been established on the basis of the results of IR,¹H and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 225–229, March–April, 1988.     

Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tellurium(IV) by cerium(IV)

The reaction is zero order in cerium(IV), fractional order in tellurium(IV) and first oder in ruthenium(III). While the ionic strength has no effect, the rate increases with increasing [H⁺], and decreases with increasing [HSO ₄ ^– ]. H and S are 54.4 kJ mol^–1 and –60.3 JK^–1 mol^–1, respectively. A suitable mechanism is proposed.

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(IV), (IV) (III). , [H⁺] [HSO ₄ ^– ]. H S 54,4 ^–1 –60,3 ·^–1·^–1, . .

     

Thermogravimetric study of dehydration of Ca(NO3)2 · CO(NH2)2 · 3 H2O under quasi-isothermal-quasi-isobaric conditions

Conventional thermoanalytical curves provide little information on the thermal decomposition of Ca(NO₃)₂ · CO(NH₂)₂ · 3 H₂O. In contrast from quasi-isothermal-quasi-isobaric thermogravimetric curves the mechanism can easily be interpreted. After the complex melts at 60°C, the solution formed is weight constant up to 135°C in the labyrinth crucible. The solution begins to boil at 135°C and gradually loses water, its boiling point increasing. The solution becomes saturated at 200°C. Thereafter, Ca(NO₃)₂ · CO(NH₂)₂ separates out while the boiling point does not change. After the departure of the water, the CO(NH₂)₂ immediately decomposes and Ca(NO₃)₂ remains.In an open crucible the above transformation is complicated by decomposition of typeAB _(s)=A _(s)+B _(g) solution evaporation drying of solid residue, surface crust formation, etc. In conventional thermoanalysis the latter processes accompany the above processes (melting-solution formation-loss of water during boiling) which hampers interpretation of the conventional curve.

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Zusammenfassung Herkömmliche thermoanalytische Kurven liefern wenig Informationen über die thermische Zersetzung von Ca(NO₃)₂ · CO(NH₂)₂ · 3 H₂O. Quasi-isotherme/quasi-isobare thermogravimetrische Kurven dagegen ermöglichen leicht eine Interpretation des Mechanismus. Nach dem Schmelzen des Komplexes bei 60°C bleibt das Gewicht der Lösung im Labyrinthtiegel bis 135°C konstant. Die Lösung beginnt bei 135°C zu sieden und verliert zunehmend an Wasser, wobei der Siedepunkt ansteigt. Die Lösung erreicht den Sättigungspunkt bei 200°C. Danach scheidet sich Ca(NO₃)₂ · CO(NH₂)₂ ohne weitere Veränderung des Siedepunktes ab. Nach Entfernung des Wassers zersetzt sich das CO(NH₂)₂ sofort und Ca(NO₃)₂ bleibt zurück.In einem offenen Tiegel wird die obige Umwandlung durch Zersetzung des TypesAB _(s)= =A _(s)+B_(g), durch Verdampfung der Lösung, durch Trocknung des festen Rückstandes, durch Oberflächenverkrustung usw. kompliziert. Diese Prozesse begleiten bei der herkömmlichen Thermoanalyse die oben erwähnten Vorgänge (Schmelzen-Lösungsbildung-Wasserverlust durch Sieden), wodurch die Interpretation der herkömmlichen Kurven erschwert wird.

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(N₃)₂·(N₂)₂·3 ₂O . , - , . 60° 135°. 135° . - 200°. , (N₃)₂ · (N₂)₂ . , . , AB_pac.=A_pac + B_pac., , , .. : — — , .

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The authors are indebted to Prof. E. Bulewicz and Prof. E. Pungor for valuable discussions.They thank Mrs. M. Kiss and Miss I. Fábián for technical assistance.     

Synthesis of thymidine 5′-(β-l-mannopyranosyl) and (4,6-dideoxy-l-lyxo-hexopyranosyl) pyrophosphates

Conclusions We have prepared thymidine 5-(-L-mannopyranosyl pyrophosphate), thymidine 5-(4,6-dideoxy--L-lyxohexopyranosyl pyrophosphate), and thymidine 5-(4,6-dideoxy--L-lyxo-hexopyranosyl pyrophosphate), all analogs of thymidine 5-(-L-rhamnopyranosyl pyrophosphate), which is involved in the biosynthesis of the O-specific chains ofSalmonella lipopolysaccharides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2588–2591, November, 1976.     

Thermodynamics and thermochemistry of kinetic (real) phase diagrams involving solids

A theoretical analysis of the formation of materials with metastable microstructures under non-ideal and highly non-equilibrium conditions is presented.

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Zusammenfassung Es wird eine theoretische Untersuchung der Bildung von Stoffen mit metastabilen MikroStrukturen unter nichtidealen Bedingungen weitab vom Gleichgewicht dargelegt.

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