Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.     

Negativer linearer thermischer Ausdehnungskoeffizient von verstrecktem Polyäthylen

Zusammenfassung Der lineare thermische Ausdehnungskoeffizient von linearem Polyäthylen hoher Dichte wurde im Temperaturbereich –20 °C bis + 40°C bestimmt. Bei isotropen Proben besteht eine lineare Beziehung zwischen Dichte bzw. Kristallisationsgrad _v und. Die gemessenen Koeffizienten liegen fürT ₀ = 20 °C im Bereich = 110 ... 130 · 10^–6 K^–1.Kalt verstreckte Proben mit Verstreckungsgraden = 8 ... 15 haben beiT ₀ = 20 °C in Verstreckrichtung den Koeffizienten _l = –24 · 10^–6 K^–1. Der negative Zahlenwert von _tl ist unabhängig von und weiteren Herstellungsparametern. Seine Ursache ist einerseits die Orientierung derc-Achsen der Kristallite in Verstreckrichtung mit _c = –12 · 10^–6 K^–1 und andererseits der negative Koeffizient _am * –50 · 10^–6 K^–1 der verspannten amorphen Phase, der auf dem gummielastischen Verhalten der tie-molecules beruht.Beim Tempern oberhalb von +40 °C schrumpfen die Proben irreversibel, wobei _| ansteigt und nach dem Aufschmelzen der Proben wieder den Wert des isotropen Materials annimmt. Nach dem Tempern wenig unterhalb der Schmelztemperatur der Kristallite wurden überhöhte Koeffizienten _| gemessen, die eine Rotation der Kristallite um dieb-Achsen erkennen lassen.

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Summary The linear thermal coefficient of expansion,, of high density linear polyethylene has been determined in the temperature range of –20 ° ... + 40 °C. For isotropic samples a linear relationship between density or crystallinity _v and is valid. Measured values of forT ₀ = 20 °C amount to = 110 ... 130 · 10^–6 K^–1.Cold drawn samples of draw ratios = 8 ... 15 yield _| = –24 · 10^–6 K^–1 atT ₀ = 20 °C parallel to the draw axis. The negative value of _| does not depend on draw ratio or other parameters of sample processing. It is caused byc-axis orientation of the crystallites in draw direction with _c = –12 · 10^–6 K^–1 and by a negative coefficient _am * = –50 · 10^–6 K^–1 of the stressed amorphous phase, which is due to rubber elastic behaviour of the tie molecules.When annealed above 40 °C the samples shrink irreversibly and _| is augmented. After melting the samples the value of isotropic material is restored. Annealing the samples little below the melting temperature of the crystallites leads to superelevated values all which reflect| rotation of the crystallites around theb-axis.

     

Steroid glycosides from the starfish Crossaster papposus

Two new steroid glycosides have been isolated from an ethanolic extract of the starfishCrossaster papposus — crossasterosides P₁ and P₂. On the basis of chemical transformations and spectral characteristics, the structure of crossasteroside P₁ has been established as (24R)-24-ethyl-5-cholestane-3,6,8,15,16,29-hexaol 29-O-[2-O-methyl--D-xylopyranosyl-(1 2)--D-galactofuranoside]. Crossasteroside P₂ is its 4-hydroxy analogue.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 669–673, September–October, 1989.     

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.     

Electronic structure of monosubstituted benzenes and X-ray emission spectroscopy

The electronic structure of the benzaldehyde molecule has been studied by X-ray emission spectroscopy. The gas-phase O-K- and C-K-spectra of this compound have been obtained. MNDO quantum-chemical calculations have been carried out. The structure of the MO's of benzaldehyde has been compared with those of benzene and formaldehyde molecules. The character of the p-p interaction of the phenyl and formyl fragments has been considered. The contribution of the latter to the highest occupied molecular orbitals of the-system has been shown to be small.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1033–1037, June, 1994.     

The identification of small amounts of sugars by means of X-ray diffraction patterns

Summary The identification of small amounts of sugars by their X-ray powder diagrams is suggested as a most simple and practical method in routine analysis.It is especially valuable in working with minute amounts of material, and has proved very useful for the final identification of chromatographically-separated sugars.The characteristics of the powder diagrams of a number of monosaccharides of special interest to the physiological chemist are reported in detail. The substances thus investigated are- and-D-glucose and-glucose monohydrate,- and-D-galactose,- and-D-mannose,D-fructose,D-glucuronolactone,- and-D-glucosamine hydrochloride,- and-D-galactosamine (chondrosamine) hydrochloride,-L-fucose, andD-ribose. For various reasons arabinose, lyxose, and xylose have also been included.It is clear from the powder diagrams of the galactoses that the crystalstructure earlier ascribed to-galactose is that of-galactose.A single-crystal study of-glucosamine hydrochloride was carried out by theWeissenberg technique. The crystal-dimensions obtained agree with those earlier found byCox et al^{5, 7}.The optical rotation of chondrosamine hydrochloride was found to be [] _D ^20° = - 135° - 93° - 39°, the first value being considerably higher than that given for the-form byLevene. A method for the preparation of-mannose is described.

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Zusammenfassung Die Identifizierung kleiner Mengen verschiedener Zuckerarten mit Hilfe ihrer Röntgen-Pulverdiagramme wird als einfache und praktische Routinemethode vorgeschlagen.Diese Methode ist besonders wertvoll, wenn nur kleine Substanzmengen zur Verfügung stehen, und hat sich für die endgültige Identifizierung von chromatographisch getrennten Zuckern als sehr geeignet erwiesen.Die Einzelheiten der Pulverdiagramme folgender physiologisch-chemisch bedeutungsvoller Monosaccharide werden mitgeteilt:- und-D-Glukose und Glukosehydrat,- und-D-Galaktose,- und-D-Mannose,D-Fruktose,D-Glukuronolakton,- und-D-Glukosaminhydrochlorid,- und-D-Galaktosamin-(Chondrosamin)-hydrochlorid,-L-Fukose, dieD-Pentosen Arabinose, Lyxose, Ribose und Xylose.Aus den Pulverdiagrammen der Galaktosen geht deutlich hervor, daß die Krystallstruktur, die früher der-Galaktose zugeschrieben wurde, tatsächlich diejenige der-Form ist.Die Untersuchung eines Einzelkristalles von-Glukosaminhydrochlorid wurde nach derWeissenberg-Technik ausgeführt. Die erhaltenen Werte stimmen mit den früher vonCox und Mitarbeitern gefundenen überein.Die optische Drehung des Chondrosaminhydrochlorids wurde zu [] _D ^20° = + 135° + 93° + 39° gefunden. Der erstgenannte Wert ist größer als der entsprechende, vonLevene angegebene Drehungswert.Eine Methode zur Darstellung von-Mannose wird beschrieben.

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Résumé On propose une méthode de routine simple et pratique pour l'identification de petites quantités de divers sucres au moyen de leur diagramme de poudres aux rayons X. Cette méthode est particulièrement précieuse quand on n'a que de petites quantités de matière à sa disposition et elle s'est montrée très convenable pour l'identification finale de sucres séparés par chromatographie. Des particularités des diagrammes de poudres des monosaccharides suivants intéressent le chimiste physiologiste: et-D-glucose et hydrate de glucose, et-D-galactose, et-D-mannose, D-fructose,D-glucuronolactone, chlorhydrate d' et-D-glucosamine, chlorhydrate d' et-D-galactosamine (chondrosamine), l'-L-fucose, lesD-pentoses, l'arabinose, le lyxose, le ribose, le xylose. Des diagrammes de poudres des galactoses découle clairement le fait que la structure cristalline qui fut attribuée précédemment à l'-galactose est celle de la forme. L'expérience sur un cristal unique de chlorhydrate d'-glucosamine a été effectuée d'après la technique deWeissenberg. Les valeurs obtenues concordent avec celles trouvées précédemment parCox et ses collaborateurs. Le pouvoir rotatoire du chlorhydrate de chondrosamine a été trouvé égal à _D ²⁰ = + 135° + 93° + 39°. La première valeur est plus grande que celle donnée parLevene. On décrit une préparation de l'-mannose.

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With 3 figures.     

Synthesis of substituted hydroxypyrazines

Conclusions A new method was developed for the synthesis of substituted hydroxypyrazine derivatives by reacting the hydrochlorides of-amino ketones with the acid chlorides of N-phthaloyl--amino acids in acetone in the presence of diethylaniline, and subsequent treatment of the intermediate N-(N-phthaloyl--aminoacyl)--amino ketones with aqueous sodium acetate solution at 100°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2417–2421, October, 1978.     

Schiff bases in syntheses of substituted naphthylamines,naphthyridines, azaphenanthrenes,and benzocarbazole

9-Methylnaphtho[2,1-b][1,6]naphthyrldine and 2,3-dimethyl-1-azaphenanthrene were obtained on a K-16 dehydrogenating catalyst from N-(1,2,5-trimethyl-4-piperidylidene)--naphthylamine, while N-cyclohexylidene--naphthylamine yielded N-phenyl--naphthylamine and benzo[a]carbazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1400–1403, October, 1972.     

A study of nitrogen- and sulfur-containing heterocycles

The reduction of -cyanoacylurethanes in an aqueous medium in the presence of hydrochlorides of aromatic amines and Raney nickel has given -arylaminoacryloyl-and -alkyl--arylaminoacryloylurethanes which have been converted by heating with 10 % aqueous caustic alkalis into 1-aryl-and 5-alkyl-1-aryluracils.For Communication X, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1088–1091, August, 1970.     

The effect of gamma-irradiation on the thermal decomposition of anhydrous cadmium nitrate

The thermal decomposition of -irradiated anhydrous cadmium nitrate was studied by dynamic thermogravimetry. The reaction order, activation energy, frequency factor and entropy of activation were calculated by the Coats-Redfern method and were compared with those of the unirradiated salt. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. The mechanism of the decomposition of unirradiated and irradiated anhydrous cadmium nitrate follows the Mampel equation: -ln(1-) for g() and the rate-controlling process is random nucleation with the formation of a nucleus on every particle.     

Über die roten Anile, 3. Mitt.

Zusammenfassung Nach dem -Ketocarbonsäureaufbauverfahren vonF. Kröhnke ² wurde aus der -[2,3,4,4-Tetramethoxy-5-brom-diphenylyl-(6)]-propionsäure das -(p-Dimethylaminophenylimino)--keto--[2,3,4,4-tetramethoxy-5-brom-diphenyl-(6)]-valeriansäurenitril (VIII) aufgebaut, das zu der -Keto--[2,3,4,4-tetramethoxy-5-brom-diphenyl-(6)]-buttersäure gespalten werden konnte. Für die -[2,3,4,4-Tetramethoxy-5-brom-diphenylyl-(6)]-propionsäure wurde eine neue Darstellungsmethode ausgearbeitet.2. Mitt.:J. Michalský undM. Smr, Mh. Chem.90, 458 (1959).     

Cell-Specific Gene Transfer by α-Cyclodextrin Conjugates with Mannosylated Polyamidoamine Dendrimers

To improve the activity and the cell specificity of gene transferof polyamidoamine starburst dendrimer, we prepared -CyD conjugates with mannosylateddendrimers (generation 2 (G2), man--CDE conjugates) having various degrees of substitution(DS) of mannose residue. The man--CDE conjugates (DS 1, 3 and 5) formed complexeswith plasmid DNA (pDNA), but man--CDE conjugate (DS 8) did not. The gene transferactivity of man--CDE conjugates (DS 1, 3 and 5) and -CDE conjugate was augmented with an increasein the charge ratio of vector/pDNA, without showing cytotoxicity. Man--CDE conjugates(DS 3 and 5) showed higher gene transfer activity than -CDE conjugate in A549 cells, whichrecognize mannose, but man--CDE conjugates (DS 1 and 8) showed almost comparable gene transfer activityto -CDE conjugate (G2). On the other hand, no appreciable enhancing effect of man--CDEconjugates (DS 3 and 5) on the transfer activity was observed in NIH3T3 cells, which do not recognizemannose. These findings suggest that man--CDE conjugates (DS 3 and 5) can be new preferablecell-specific non-viral vectors of pDNA to cells which recognize the mannose moiety.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon und i-Butyrophenon

Zusammenfassung Bei der Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon undi-Butyrophenon entstehen die entsprechenden Thiazoline-(3), deren saure Hydrolyse zu -Mercaptopropiophenon, -Mercapto-n-butyrophenon bzw. -Mercapto-i-butyrophenon führt. Die Dehydrierung dieser -Mercaptoketone mit Schwefel zu Di- bzw. Trisulfiden wird beschrieben. Die Kondensation der -Mercaptoketone mit Ammoniak und einer Oxokomponente führt zu neuen Thiazolinen-(3), von denen die in 2- und 5-Stellung monosubstituierten Vertreter sich mittels Schwefel zu Thiazolen dehydrieren lassen.

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The interaction of sulfur and ammonia with propiophenone,n-butyrophenone andi-butyrophenone leads to the corresponding thiazolines-(3). On acid hydrolysis of the latter -mercaptopropiophenone, -mercapto-n-butyrophenone and -mercapto-i-butyrophenone respectively are formed. The dehydrogenation of these -mercaptoketones with sulfur to di- and trisulfides respectively is described. The condensation of the -mercaptoketones with ammonia and oxo-components yields new thiazolines-(3) of which the 2- and 5-monosubstituted compounds can be dehydrogenated to thiazols with elementary sulfur.

     

The O-nitration of tertiary unsaturated alcohols andα-epoxyalcohols

Conclusions The method for O-nitrating unsaturated alcohols and-epoxyalcohols has been extended to tertiary alcohols;, -dimethylallyl and, ;-dimethylglycidyl nitrates have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1354–1355, June, 1967.     

Conversion of hydrocarbons on supported catalysts prepared via decomposition of surface complexes. Preparation and properties of (Ga+Pt)/SiO2 and (Ga+Pt)/Al2O3 catalysts

The addition of gallium is shown to increase Pt dispersity and its stability to deactivation in n-hexane dehydrocyclization, to decrease the rate of n-hexane hydrogenolysis and to increase the selectivity to benzene, apparently, due to the interaction of Pt clusters with surface Ga ions.

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, -, - . .

     

Application of thermal analysis for quantitative nitrogen determination in fertilizers

DSC and DTA techniques have been used to determine nitrogen present in the form of ammonium nitrate in fertilizers. The optimum conditions for the investigations were determined for both techniques. By determining peak area, i.e. the enthalpy of the ammonium nitrate crystal transformation II I, it was possible to determine the nitrogen content in ammonium nitrate and in lime ammonium nitrate by DSC with average deviations of 0.44 and 0.91%,respectively. Using DTA and the enthalpy of the ammonium nitrate crystal transformation IV III, the average deviation of nitrogen determination in lime/ammonium nitrate was 1.09%.

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Zusammenfassung DSC und DTA wurden zur Bestimmung des in Düngemitteln in Form von Ammoniumnitrat vorliegenden Stickstoffs benutzt. Für beide Techniken wurden die optimalen Untersuchungsbedingungen ermittelt. Durch Bestimmung der Peakfläche, d. h. der Enthalpie der Kristalltransformation II I des Ammoniumnitrats konnte der Stickstoffgehalt in Ammoniumnitrat und in Kalk/Ammoniumnitrat mittels DSC mit mittleren Abweichungen von 0.44 bzw. 0.91% bestimmt werden. Aus der Kristalltransformation IV III des Ammoniumnitrats ergibt sich bei Benutzung der DTA-Methode eine mittlere Abweichung von 1.09% für die Stickstoffbestimmung in Kalk/Ammoniumnitrat.

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, . . , , (III) , — . , , 0,44 0,91%. IVIII , - 1,09%.

     

Methyl γ-phenylacetoacetate in the synthesis of derivatives of α-aminoindol-2-yl-acetic acid

The cyclization of the di(phenylhydrazone) of methyl -phenyl-,-dioxobutyrate with hydrazines has given phenylhydrazones of methyl indol-2-ylglyoxylates, which have been reduced to methyl -aminoindol-2-ylacetates. Some reactions of these compounds have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1040–1042, August, 1973.     

Thermochemistry of Carbonization of Polypyromellitimide

The mechanisms of thermal degradation processes in polypromellitimide films were investigated by mass-spectrometric thermal analysis and high-resolution NMR spectroscopy in the solid state. Both the structures of the solid residues of pyrolysis products of the PM polyimide and the process of carbonization proper up to 1200° were studied. It was established that the breaking of the C_ar-O-C_ar bond in the diamine moiety is not the primary act of degradation of the molecular structure of the polymer, as might be expected on the basis of the value of the bond energy. The process of intermolecular crosslinking following polymer degradation under high-temperature conditions is completed by the formation of a complex nitrogen-containing heterocyclic structure.

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Zusammenfassung Der Mechanismus der in Polypyromellitfilmen ablaufenden thermischen Zersetzungsprozesse wurde durch massenspektrometrische thermische Analyse und hochauflösende Festkörper-NMR-Spektroskopie untersucht. Sowohl die Struktur des festen Rückstandes des Pyrolyseproduktes des PM-polyamids als auch der Prozeß der Verkokung bis 1200 °C wurden Untersucht. Es wurde festgestellt, daß das Aufbrechen der Bindung C _ar ,-O-C _ar im Diaminteil nicht der primäre Schritt der Zersetzun der molekularen Struktur des Polymers ist, wie nach dem Wert der Bindungsenergie zu erwarten wäre. Der auf die Hochtemperatur-Polymerzersetzung folgende Prozeß der intermolekularen Vernetzung endet mit der Bildung einer komplexen stickstoffhaltigen heterozyklischen Struktur.

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- (MTA) (MP BPTT) , 1200 °C. . , C _ap -C _ap , , .

     

Ring opening of fluoroalkyl-containing α,β-epoxyketones by aromatic amines

Aromatic amines cause ,-epoxyketones containing a -fluoroalkyl group to undergo ring opening at the -position to give -amino--hydroxyketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 882–883, May, 1994.