Determination of α and β parameters in approximate SCF MO theories

The formula proposed by Linderberg for the evaluation of the resonance integral is further investigated. Consistency requirements for the parameters lead to an explanation of the Wolfsberg-Helmholz form for. The simple assumption that is proportional to the overlap integral is improved. The dependency of a and values on the distance in a diatomic molecule in this approximation is presented and discussed.

---

Zusammenfassung Linderbergs Formel zur Berechnung des Resonanzintegrals wird weiter untersucht. Konsistenzforderungen für die-Parameter führen zu einer Erklärung der Wolfsberg-Helmholz-Form für. Die einfache Annahme, daß dem Überlappungsintegral proportional ist, wird verbessert. Die Abhängigkeit von- und-Werten vom Atomabstand in einem zweiatomigen Molekül wird in dieser Näherung angegeben und diskutiert.

---

Résumé Etude de la formule proposée par Linderberg pour le calcul de l'intégrale de résonance. Des nécessités de cohérence pour les paramètres conduisent à une explication de la formule de Wolfsberg-Helmholz pour. L'hypothèse simple selon laquelle est proportionnel à l'intégrale de recouvrement est améliorée. On présente en la discutant la dépendance à la distance des valeurs de et de dans une molécule diatomique dans cette approximation.

     

Détermination spectrophotométrique de l'analgène au moyen de chlorure de fer(III) et d'α,α'-dipyridyle

Résumé On a élaboré une méthode spectrophotométrique de détermination de l'analgène au moyen de chlorure de fer-III et de l',-dipyridyle. En milieu alcalin, l'analgène réduit le fer-III en fer-II. L',-dipyridyle forme avec le fer-II un composé complexe rouge vif. La densité optique de la solution analysée est proportionnelle à la concentration de l'analgène. On effectue les mesures à 520 nm. Dans l'analyse de 18 substances pharmaceutiques, la détermination de l'analgène fut gêne par le phénylbutazon (le rapport étant supérieur à 1 1) et par le pyramidon.

---

Spectrophotometric determination of Analgene by means of iron(III) chloride and ,'-dipyridyl

Summary A spectrophotometric method of determining Analgene by means of iron(III) chloride and, dipyridyl has been worked out. The analgene (in alkaline medium) reduces the Fe(III) to Fe(II). The,-dipyridyl produces a bright red complex compound with Fe(II). The optical density of the solution being analyzed is proportional to the concentration of the analgene. The measurement is made at 520 nm. In 18 pharmaceutical preparations, the determination of the analgene was impaired by phenylbutazone (ratio above 1 1) and by pyramidon.

---

Zusammenfassung Eine spektrophotometrische Methode zur Bestimmung von Anaigen [1-Phenyl-2,3-dimethyl-4-(N-methyl-N-methansulfonsäure)-5-pyrazolon] mit Hilfe von Eisen(III)-chlorid und,-Dipyridyl wurde ausgearbeitet. In alkalischem Milieu reduziert Anaigen das Eisen zur zweiwertigen Stufe; dieses bildet dann mit,-Dipyridyl einen lebhaft rot gefärbten Komplex. Die Farbintensität ist der Konzentration proportional. Sie wird bei 520 nm gemessen. Unter 18 geprüften pharmazeutischen Substanzen wird die Reaktion von überschüssigem Phenylbutazon sowie von Pyramidon gestört.

     

Analogs of pyrimidine nucleosides

N₁-(-Tetrahydrofuranyl)- and N₁-(-tetrahydropyranyl)uracils and the corresponding 6-azauracils have been obtained by the condensation of bistrimethylsilyl derivatives of uracils and 6-azauracils with-chlorotetrahydrofuran and-chlorotetrahydropyran. The superiority of the silyl method over the mercury method used previously has been demonstrated.For part III, see [9].     

The electronic structure of angular polyphenes

SCF calculations of molecular orbitals and electronic transition energies for angular polyphenes of two through nine benzene rings have been made. The calculated sequences of the singlet and triplet energies of the , , , and p bands (Clar's notation) are compared to the limited available experimental data.

---

Zusammenfassung PPP-Rechnungen mit begrenzter Konfigurationenwechselwirkung wurden für die Reihe der angular anellierten Polyphene durchgeführt. Die berechneten -, -, - und p-Banden werden mit den wenigen vorhandenen experimentellen Daten verglichen.

---

Résumé Calculs SCF des orbitales moléculaires et des énergies de transition électronique pour les polyphenés angulaires de deux à neuf cycles benzeniques. Les séries calculées pour les énergies singulet et triplet des bandes -, -, et p (notation de Clar) sont comparées aux quelques données expérimentales disponibles.

     

Triterpene glycosides ofCauliphyllum robustum. The structures of caulosides B and C

Summary Two triterpene glycosides — caulosides b and c — have been isolated from a methanolic extract of the leaves ofCaulophyllum robustum maxim. Cauloside b has been identified as hederagenin 3--L-rhamnopyranosyl-(12)--L-arabinopyranoside, while cauloside c has the structure of hederagenin 3-0--L-arabinopyranosyl(13)--L-pyranosyl-(12)--L-arabinopyranoside.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–176, March–April, 1979.     

Synthesis and study of L-arabinopyranosides of 5- and 6-nitroindoles

Condensation of 5- or 6-nitroindoline with L-arabinose gave 1--L-arabinopyranosyl-5 (or 6)-nitroindolines, which, after acetylation, dehydrogenation, and removal of the protective groups, are converted to 1--L-arabinopyranosyl-5(or 6)-nitroindoles and then to the corresponding amino derivatives. 1--L-Arabinopyranosyl-6-nitro-3-bromo-(iodo)indoles were obtained. The selective 2-O- and 3-O-deacetylation of 1-(2, 3, 4-tri-O-acetyl)--L-arabinopyranosyl-6-nitroindole was accomplished.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 224–229, February, 1979.     

Circular Dichroism Spectra of 5- and 7-Bromo-6-ketosteroids

Circulardichroismspectra of 5- and 7-bromo-6-ketosteroidsof the cholestane and stigmastane serieswere studied. A negative Cotton effect corresponding to the n-* -transition of the ketone was observed in the CD spectra of 5-bromo-6-ketosteroids at 300 nm. The analogous Cotton effect was positive in CD spectra of 7-bromo-6-ketosteroids.     

Thermal decomposition of organic derivatives of crystalline zirconium phosphate

The diethylene glycol, benzyl alcohol and benzylamine derivatives of- and-zirconium phosphates were prepared and their thermal behaviour was investigated by means of differential thermal analysis. In all cases, the derivatives of-zirconium phosphate were more stable than those of-zirconium phosphate.

---

Zusammenfassung Es wurden Diethylenglykol-, Benzylalkohol- und Benzylamin-Derivate von- und-Zirkoniumphosphaten hergestellt und ihr Thermisches Verhalten mittels DTA untersucht. In allen Fällen waren die Derivate der-Zirkoniumphosphate stabiler als die der-Zirkoniumphosphate.

     

Zusammenhang zwischen den K α-Satelliten-Linien und den Röntgenübergängen vom Typ K 1 L 1→L 2 bei den Elementen Neon,Natrium, Magnesium,Aluminium und Silizium

Zusammenfassung Für die Elemente Neon, Natrium, Magnesium, Aluminium und Silizium werden mit einem quantenmechanischen Variationsverfahren unter Verwendung einer minimalen STF-Funktionenbasis Röntgenübergänge vom Typ K ¹L¹L² berechnet und den K -Satellit-Linien , , ₃, ₃ and ₄ zugeordnet.

---

Relation between K -Satellits and X-ray-transitions of the type K ¹ L ¹L ² for Ne, Na, Mg, Al and Si

STF-Calculations are reported for X-ray-transitions of the type K ¹L¹L² for Ne, Na, Mg, Al and Si. It is shown that these transitions are correlated with the K -satellits , , ₃, ₃ and ₄.

---

---

Die Wellenfunktionen können auf Anfrage zur Verfügung gestellt werden.     

Perturbation calculation of oscillator strengths for the isoelectronic series of light atoms

Transition probabilities and oscillator strengths are calculated for the configurations 1s² 2sⁿ¹ and 1s² 2s^n1-1 2pⁿ²⁺¹, which are, respectively, of the form P=a/Z (1+/Z+) andf=/Z (1+/Z+). Numerical values are given fora, ,, and.     

Substitution of halogen atom in α-halonitro compounds of the aliphatic series

Ethyl -halo--nitropropionate and -butyrate were prepared by alkylating ammonium salts of ethyl bromo- and chloronitroacetates. The addition of alkyl acrylates to alkyl chloronitroacetates or their salts gives dialkyl -chloro--nitroglutarates. Sodium salts of ethyl -nitro--sulfo--hydroxypropionate and -butyrate were obtained by the sulfodehalogenation of ethyl -chloro--nitro--hydroxypropionate and -butyrate with sodium dithionite. Esters of -amino acid hydrochlorides were prepared by the reduction of alkyl -chloro--nitrocarboxylates. The hydrogenation of alkyl nitrosulfoacetates leads to the corresponding disodium salts of alkyl aminodisulfoacetates and piperazine-2,5-dione.For communication 5 seeIvz. Akad. Nauk SSSR, Ser. Khim., 1990, 2012 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990,39, 1826].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 872–876, May, 1994.     

Chemistry of heteroanalogs of isoflavones

3-Hetaryl-7-methoxychromones were obtained by reaction of -(5-ethoxycarbonyl-2-furyl)-, -(2-benzofuryl)-, and -(2-methoxy-carbonyl-5-benzofuryl)-2-hydroxy-4-methoxyacetophenones with methyl formate or ethyl orthoformate, and 3-hetaryl-4-hydroxy-7-methoxy-coumarins were obtained by reaction of the same compounds with diethyl carbonate. Methods for the synthesis of 3-hetaryl-7-hydroxy-chromones from -furyl- and -benzofuryl-substituted, 2,4-dihydroxyacetophenones were investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 174–179, February, 1975.     

Steroid glycosides of the seeds ofNicotiana tabacum. II. The structures of nicotianosides C and F

From the seeds of tobacco Nicotiana tabacumL. we have isolated two new steroid glycosides, nicotianosidesC andF. The structures of the glycosides have been shown on the basis of chemical transformations and spectral characteristics. Nicotianoside C is a steroid glycoside of the spirostan series and has the structure of (25S)-5-spirostan-3ß-ol3-O-[-L-rhamnopyranosyl-(1 2)]-[-L-rhamnopyranosyl-(1 4)]-ß-Dglucopyranoside), and nicotianoside F is (25S)-5 furostan-3ß, 22, 26-triol 3-O-[-L-rhamnopyranosyl-(1 2)1-[-L-rhamnopyranosyl-(1 4)1-ß D-glucopyranoside) 26-O-ß-D-glucopyranoside.Institute of Genetics, Academy of Sciences of the Republic of Moldova, 277022, Kishinev, ul. Pédurilor, 20. Translated Khimiya Prirodnykh Soedinenii, No. 3, pp. 396–401, May–June, 1995. Original article submitted August 29, 1994.     

The incompleteness of Rényi entropies

Since the advent of the notion of mixing character in statistical mechanics, it has been conjectured over and over again that the Rényi entropies provide a mixing isomorphic family, that is: given two probability distributions p and q, the mixing character of q exceeds that of p, m[q]> m[p], if and only if I (q)I (p) for any positive . This conjecture is disproved by means of counterexamples.     

1H-NMR Studies of the Inclusion Complexes between α-Cyclodextrin and Adamantane Derivatives Using Both Exchangeable Hydroxy Protons and Non-Exchangeable Aliphatic Protons

The inclusion complexes between -cyclodextrin (-CD) and adamantane, 1-adamantanol, 1-(hydroxymethyl)-adamantane, 2-adamantanol, and 1,3-adamantanediol in aqueous solution have been studied by ¹H-NMR spectroscopy using both non-exchangeable and exchangeable protons. The complexation-induced ¹H-NMR shifts (CIS) and NOEs of non-exchangeable protons, as well as the CIS, NOEs, temperature coefficients, and linewidth of signals from exchangeable hydroxy protons have been determined. The stoichiometry of the adamantane/-CD complex could not be determined due to the low solubility of adamantane. However, for 0.11 equivalent of adamantane added, two sets of separate ¹H signals for the free and bound -CD were observed. The signal from O(3)H in the complexed form appeared narrow and upfield shifted with a low-temperature coefficient indicating reduced hydration inside the hydrophobic cavity of -CD. Both 1-adamantanol, and 1-(hydroxymethyl)-adamantane formed 1:1 inclusion complexes with -CD and only one set of NMR signals was observed. The CIS and NOEs suggested that both complexes had similar structures. The O(2)H signal of -CD was broadened at low temperature and became narrower as the temperature raised. The broadening increased with higher concentration of guest suggesting interaction between O(2)H of -CD and the guest molecules. The stoichiometry of the -CD/2-adamantanol complex could not be determined with certainty, but the NMR data suggested equilibrium between 2:1 and 1:1 complex. As with adamantane, a sharp and upfield shifted O(3)H signal with a very low-temperature coefficient was observed. No inclusion complex was formed between 1,3-adamantanediol and -CD. This study showed how the hydroxy protons of -CD could be used to obtain complementary information on the geometry and stability of inclusion complexes of -CD.     

Chromatographie d'élution des aminoacides et de leurs dérivés sur colonne d'échangeurs d'ions à trame hydrophile

Sommaire Le comportement chromatographique des dansylaminoacides hydrosolubles (acide dansylcysteique, -monodansylarginine, -monodansylhistidine, -monodansyllysine, -monodansyllysine), des aminoacides correspondants, et du dansylacide sur colonne d'échangeur de cation à trame hydrophile (Phospho-cellulose, Sulfoéthyl-dextrane réticulé) est rappelé. Les monodansyldérivés de l'arginine, de l'histidine, de la lysine peuvent être isolés à l'état pur de leur milieu de formation par un procédé chromatographique employant ces échangeurs de cations. L'acide dansylcysteique, non retenu (comme le dansylacide) par ces échangeurs de cations, peut être séparé du dansyl-acide et de l'acide cysteique, par chromatographie sur colonne de Diéthylaminoéthyldextrane réticulé. Un procédé chromatographique similaire permet de séparer les deux dérivés monodansylés de la lysine.

---

Elution chromatography of aminoacids and their derivatives on an ion exchange column with hydrophilic cross-linkagePart 2: Behaviour of water-soluble dansylamino acids on an ion exchange column of cross-linked DEAE dextrane

Summary The chromatographic behaviour of water soluble dansylamino acids (dansylcysteic acid, -monodansyl arginine, -monodansyl histidine, -monodansyl lysine, -monodansyl lysine), of the corresponding amino-acids, and of dansyl acid on a cation exchange column with hydrophilc crosslinks (Phosphocellulose, cross-linked Sulfoethyl dextrane) is reported. The monodansyl derivatives of arginine, histidine, and lysine can be isolated in pure form from the medium in which they have been formed, by means of a chromatographic procedure using these cation exchangers. Dansylcysteic acid. Which is not retained (like dansyl acid) by these cation exchachangers, can be separated from dansyl acid and from cysteic acid by chromatography on a column of cross-linked diethyl aminoethyl dextrane. A similar chromatographic process permits the separation of the two monodansyl derivatives of lysine.

---

Elutions-Chromatographie von Aminosäuren und ihren Derivaten auf einer Ionenaustauscher-Säule mit hydrophiler Füllung2. Teil: Verhalten der hydro-säurelöslichen Dansylaminosäuren auf einer Ionenaustauscher-Säule mit vernetztem DEAE-Dextran

Zusammenfassung Es wird an das chromatographische Verhalten der hydrolöslichen Dansylaminosäuren (Dansyl-Cysteinsäure, -Monodansyl-arginin, -Monodansyl-histidin, -Monodansyl-lysin, -Monodansyl-lysin) sowie der entsprechenden Aminosäuren und von Dansylsäure auf einer Kationenaustauscher-Säule mit hydrophiler Füllung (Phospho-cellulose, vernetztes Sulfoäthyldextran) erinnert. Durch ein chromatographisches Verfahren mit derartigen Kationen-Austauschern lassen sich die Monodansylderivate von Arginin, Histidin und Lysin im Reinzustand aus ihrem Entstehungs-Medium isolieren. Die nicht (wie die Dansylsäure) von diesen Kationenaustauschern zurückgehaltene Dansylcysteinsäure kann durch Chromatographie auf einer Säule mit vernetztem Diäthylaminoäthyldextran von der Dansylsäure und der Cysteinsäure getrennt werden. Durch ein ähnliches chromatographisches Verfahren lassen sich die beiden Monodansylderivate von Lysin trennen.

     

N-methyI-N-(triethoxysilylmethyl) andN-methyl-N-(silatran-1-ylmethyl) substituted glycine and alanine

Organosilicon derivatives of glycine, - and -alanine, and -methylalanine were prepared by the reaction of methyl esters of - and -halocarboxylic acids withN-methylaminomethyltriethoxysilane in the presence of triethylamine. The compounds synthesized were converted into the correspondingN-silatran-l-ylmethyl derivatives. Trimethylsilyliodoacetate reacts withN-methylaminomethyltrietoxysilane to give 2,2-diethoxy4-methyl-1-oxa-4-aza-2-silacyclohexane-6-one. Its reaction with triethanolamine leads toN-methyl-N-(silatran-l-ylmethyl)glycine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–343, February, 1995.     

Synthesis of α,α′-bisdialkylphosphonoisopropylnitroxyls

Conclusions Some,-bisdialkylphosphonoisopropylnitroxyl radicals were obtained by the thermolysis of dialkyl -nitrosoisopropylphosphonates and isolated in the pure state.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1867–1868, August, 1979.     

Researches on imidazoles

A study is made of the reaction of the sodium and ammonium salts of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5 mercaptoimidazoles with -halogenoketones, -halogenoalcohols, and — and -halogeno acids, to give a number of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5- [-ketoalkyl (aralkyl)-, -hydroxyethyl-, and -and -carboxyalkyl] mercaptoimidazoles.For Part XXIV see [6].     

Thermal decomposition of the addition compound of potassium carbonate with hydrogen peroxide

The kinetics of the thermal decomposition of the addition compound of potassium carbonate with hydrogen peroxide was carried out using a fixed bed flow reactor with gas-chromatography. The experimental results can be best represented over the whole range of the decomposition, by the equation-In (1–)=kt, where=degree of decomposition,t=time (min.), andk=rate constant (min.^–1). The activation energy and the pre-exponential factor for 0<<0.8, are 74.3 kJ/mol and 7.8 · 10⁹, and for the decay period (0.8<<1.0), 77.3 kJ/mol and 1.38 · 10¹⁰, respectively.

---

Zusammenfassung Die Kinetik der thermischen Zersetzung der Additionsverbindung von Kaliumcarbonat mit Wasserstoffperoxid wurde unter Anwendung eines Fixbett-Durchfluß-reaktors durch Gaschromatographie untersucht.Die Versuchsergebnisse können im ganzen Bereich der Zersetzung am besten durch die Gleichung (I) -ln (1–)=kt beschrieben werden;=Zersetzungsgrad,t=Zeit (min) undk=Geschwindigkeitskonstante (min^–1).Die Aktivierungsenergie und der präexponentielle Faktor betragen, für 0<<0.8, 74.3 kJ/Mol, bzw. 7.8 · 10⁹ und für die Periode des Abklingens (0.8<<1.0) 77.3 kJ/Mol, bzw. 1.38 · 10¹⁰.

---

Résumé On a étudié, par chromatographie en phase gazeuse, la cinétique de la décomposition thermique du composé d'addition du carbonate de potassium avec de l'eau oxygénée, en se servant d'un réacteur à écoulement, type lit fixe.Les résultats expérimentaux peuvent être décrits avec un bon ajustement dans tout l'intervalle de décomposition, par l'équation (I) -ln (1–)=kt;=degré de décomposition,t=temps (min) etk=constante de vitesse (min^–1).L'énergie d'activation et le facteur préexponentiel sont pour 0<<0.8, respectivement égaux à 74.3 et 7.8 · 10⁹ kJ/mole, et pour la période d'amortissement (0.8 <<1.0) à 77.3 et 1.38 · 10¹⁰ kJ/mole.

---

, . -ln(1–)=t, - ,t- ( .) - (.^–1). 0<<0.8, , 74.3 / 7.8. 10⁹, (0.8<<1.0) —77.3 / 1.38. 10¹⁰.

---

---

The authors wish to express their appreciation to Dr. D. Dollimore for his valuable comments and thank Mr. H. Nakamura, Research Fellow, Department of Environmental Engineering, Kyushu Institute of Technology, for his advise.