The structure of seselirin: A new chromone from the roots ofSeseli sessiliflorum

Conclusions From the roots ofSeseli sessiliflorum Schrenk a new chromone has been isolated for which the structure of 2,2-dimethyl-3-(3-methylthioacryloyloxy)-3,4-dihydropyrano-5,6:6,7-(5-hydroxy-2-methyl) chromone has been proposed. It is the first representative of this group of natural compounds containing sulfur.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 4, pp. 412–415, 1970     

Gas-chromatographic determination of the composition of the volatile components of the oleoresins of some species of conifers

Using the method of analytical GLC in a glass capillary column, the compositions have been studied of the volatile fractions of the oleoresins of five species of conifers:Larix decidua,Pinus strobus,Pinus mugo,Picea excelsa, andPinus abies. In the oleoresins 21 monoterpene and 22 sesquiterpene compounds were identified from their relative retention times and with the aid of additives. The main components of the volatile fractions of the oleoresins were - and -pinenes and 3-carene among the monoterpenes, and longifolene caryophyllene, - and -cadinenes and -murolene among the sesquiterpene compounds. The quantitative analysis of the fractions was carried out by the method of internal normalization from averaged correlation coefficients.Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 629–632, September–October, 1990.     

Synthesis of γ- dihydropyrones and β- dihydrofuranones on the basis of acetylenic γ- and δ-keto alcohols and acetals of γ- and δ-formyl alcohols

Acetylenic - and -keto alcohols and acetals of acetylenic - and -keto alcohols and acetals of acetylenic - and -formyl alcohols undergo cyclization to -dihydropyrones and -dihydrofuranones under the influence of acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1471–1473, November, 1976.     

The structure of smyrnioridin

Conclusions A new coumarin, which has been called smyrniodidin, has been isolated from the roots ofSmyrniopsis aucheri acetoxy-1-methylethyl)-4-angeloyloxy-4,5dihydrofuro-2, 3: 7, 6-coumarin. Boiss. The NMR spectrum and a study of the saponification products of smyrnioridin have shown that it is 5-(1-     

Coumarins of Seseli tenuisectum

Summary The herbSeseli tenuisectum has been found to contain — in addition to anomalin — another three coumarins (C-2, C-3, and C-4) which are derivatives of khellactone.On the basis of NMR, mass, and IR spectroscopy, the products of stepwise alkaline methanolysis and hydrolysis, and conversion into pteryxin, it has been established that two of them are isomeric monoesters of khellactone and angelic acid with the structures 3-angeloyloxy-4-hydroxy- and 4-angeloyloxy-3-hydroxy-3,4-dihydroxyseselin, respectively. They have been obtained in the individual state for the first time by thin-layer chromatography, which has enabled their IR spectra to be recorded.The lactone C-4 is a diester of khellactone with the structure 4-angeloyloxy-3-isovaleryloxy-3,4-dihydroseselin.We are the first to have found these substances in plants of the flora of the USSR.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 38–43, January–February, 1972.     

Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

Effect of α-methylstyrene of the curing behaviour of vinyl ester resins

The curing behaviour of bismethacryloxy derivative of diglycidyl ether of bisphenol A (vinyl ester resin) containing styrene as the reactive diluent (40% w/w) was studied using gel point determination method and DSC. Seven samples of styrene/-methylstyrene in the ratio 400, 355, 3010, 2515, 2020, 1525 and 040 were studied. Delayed curing was observed in samples containing increasing proportions of -methylstyrene. The energy of activation decreased from 869 kJ mol^–1 to 333 kJ mol^–1 as the concentration of -methylstyrene increased in the formulations. However, no difference in thermal stability was observed by replacement of styrene by -methylstyrene. It was concluded that in vinyl ester resin samples 10–15% -methylstyrene and 30-25% styrene can be used as reactive diluent.

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Zusammenfassung Mittels DSC und Bestimmung der Gelierungstemperatur wurde das Aushärteverhalften des Bismethakryloxyderivaten des Diglycidyläthers von Bisphenol A (Vinylesterharz) mit 40 Gewichtsprozenten Styrol als reaktives Streckmittel untersucht. Es würden sieben Proben mit einem Styrol/-Methylstyrol Verhältnis von 400, 355, 3010, 2515, 2020, 1525 und 040 untersucht. Mit steigendem Anteil an -Methylstyrol konnte eine Verzögerung der Aushärtung sowie ein Absinken der Aktivierungsenergie von 869 kJ · mol^–1 auf 333 kJ · mol^–1 beobachtet werden. Der Ersatz von Styrol durch -Methylstyrol veränderte jedoch die thermische Stabilität in keiner Weise. Vinylesterharzproben mit 10–15% -Methylstyrol und 30–25% Styrol können als reaktive Streckmittel in Vinylesterharzen verwendet werden.

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- - , 40 .% . /-, 400, 355, 3010, 2515, 2020, 1525 040. - . - 869 333 · ^–1. , .. , , 10–15% - 30–25% .

     

Temperature dependence of the volumetric properties of binary mixtures containing oxaalkane +n-heptane

Excess molar volumes of mixtures of n-heptane + 2,5-dioxahexane and n-heptane + 2,5,8-trioxanonane were determined from density measurentents at 5, 15, 25 and 35°C. These results allowed the following mixing quantities to be reported in all range of concentrations: , (v ^E /T) _P and (h ^E /P) _T , at 25°C. The obtained values were then compared with the calculated values by using the Flory theory and the Nitta-Chao theory of liquid mixtures. The results are discussed in terms of order or disorder creation.     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

Synthesis of ω-substituted 5-alkylorotic acids

The lactone of 5 - -hydroxyethylorotic acid, the thiolactone of 5-(-mercaptoethyl)orotic acid, and 5-(-benzamidobutyl)orotic acid were synthesized from substituted 5-carb-ethoxymethylenehydantoins obtained by the condensation of urea with -ethoxalyl derivatives of -butyrolactone, -thiobutyrolactone, and ethyl -benzamidocaproate. The lactam of 5-(-aminoethyl)orotic acid was synthesized by the ammonolysis of the lactone of 5 -(-hydroxyethyl)orotic acid. The acid hydrolysis of 5-(-benzamidobutyl)orotic acid gave 5-(-aminobutyl)orotic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1282, September, 1971.     

On the reduction of NiO forms in magnesia supported catalysts

Reducibility of Ni/MgO catalysts has been studied by the temperature-programmed reduction (TPR) technique in the temperature range of 373–1273 K. The profile of reduction reveals the presence of various forms of NiO. The effects of nickel loading and treatment temperature on catalyst reducibility have been evaluated. The formation of NiO–MgO solid solution controls the whole reduction of Ni/MgO system.

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Ni/MgO 373–1273 . NiO. . Ni/MgO NiO–MgO.

     

Steric substituent effect on the resin catalyzed hydrolysis of alkyl acetate esters

The rates of hydrolysis of seven acetate esters substituted in the alkyl group have been studied in the presence of a sulfonated cation exchange resin in 70% aqueous acetone solution. the slower hydrolysis rates with increasing size of substituent are related to increasing steric influence, as determined by decreasing values of the steric substituent parameter, E_s. The efficiency of the resin catalyst is related to the entropy of substituents. Influence caused by steric hindrance on reaction rates accounts satisfactorily for observed variations of the enthalpies and entropies of activation with alkyl group substituents. The entropy, S^x, values increase in the order: n-octyl-

, , 70%- . , , E_S. . , . , S^*, : --<-<, .

     

Some methoxy derivatives of 9-amino-6-nitroacridine

The reaction of the 2-, 3-, and 4-methoxy derivatives of 9-chloro-6-nitroacridine with-diethylamino--methylbutylamine and with-diethylamino--hydroxypropylainine in phenol has given the 2-, 3-, and 4-methoxy derivatives of 9-(-diethylamino--methylbutylamino)-6-nitroacridine and of 9-(-diethylamino--hydroxypropylamino)6-nitroacridine, respectively.     

Effect of the dispersity of substances on the macrokinetics of thermal analysis under non-isothermal conditions

The effect of the dispersity of the sample on the topochemical mechanism and on the kinetic parameters of thermolysis (A _sB_s + C_g) under non-isothermal conditions is discussed. For correctness of the experiment, a ratio of maximum and minimum particle diameters 6 is a necessary condition. The topochemical mechanism of the process should be determined separately for the initial and final stages.

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Zusammenfassung Die Wirkung der Dispersion der Probe auf den topochemischen Mechanismus und die kinetischen Parameter der Thermolyse (A_s B_s + C_g) unter nichtisothermen Bedingungen wird diskutiert. Die Genauigkeit des Experiments setzt ein Verhältnis der maximalen und minimalen Teilchendurchmesser von 6 voraus. Der topochemische Mechanismus sollte für die Anfangs- und Endphase des Vorganges einzeln bestimmt werden.

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Résumé L'effet de la dispersion de l'échantillon sur le mécanisme topochimique et sur les paramètres cinétiques de la thermolyse (A_s B_s + C_g) en conditions non-isothermes est discuté. La conditions nécessaire pour qu'une expérience soit correcte est que le rapport entre les valeurs maximale et minimale des diamètres des particules soit 6. Le mécanisme topochimique du processus devrait être déterminé séparément pour les étapes initiale et finale.

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(A + ) . d ./d 6; .

     

Study of the thermal behaviours of some metal acrylates

The thermal behaviours of Na, Ca, Mg and Zn acrylates were investigated by TG and DTA. It was found that the anhydrous acrylates were subject to thermal polymerization processes, which preceded the main decomposition. The presence of oxygen influences the decomposition of the organic part of the molecule very strongly, but it does not markedly affect the extent of polymerization or the type of the resulting solid products. Metal carbonates or oxides make up the major proportion of the residue obtained after the decomposition of the metal acrylates, similarly as in the case of other low molecular monocarboxylic acid salts.

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Zusammenfassung Das thermische Verhalten von Na, Ca, Mg und Zn-Akrylaten wurde mittels TG und DTA untersucht. Es wurde festgestellt, daß die wasserfreien Akrylate einen termischen Polymerisierungsproze erleiden, der der Hauptzersetzung vorangeht. Die Gegenwart von Sauerstoff wirkt sich sehr stark auf die Zersetzung des organischen Teils des Moleküls aus, beeinflut jedoch das Ausma der Polymerisierung und den Typ der entstandenen festen Produkte nicht besonders. Die bei der Zersetzung von Metallakrylaten erhaltenen Substanzen bestehen größtenteils aus Metallkarbonaten oder -oxiden, analog wie bei anderen Salzen von niedermolekularen Monokarbonsäuren.

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Résumé Etude du comportement thermique des acrylates de Na, Ca, Mg et Zn par thermogravimétrie et par analyse thermique différentielle (TG et ATD). On observe que les acrylates anhydres subissent un processus de polymérisation thermique qui précède la décomposition principale. La présence d'oxygène exerce une forte influence sur la décomposition de la partie organique de la molécule mais elle n'affecte pas de manière importante le degré de polymérisation ni la nature des produits solides formés. La majeure partie du produit obtenu après la décomposition des acrylates métalliques est constituée de carbonates et d'oxydes métalliques comme c'est le cas pour les autres sels d'acides monocarboxyliques à faibles poids moléculaires.

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TG Na, , Mg Zn. , , . , . , , , .

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The authors thank Mr. J. Bobinski for his help in translating this paper into English.     

Tetrahydrothiophene as intermediate in the hydrodesulfurization of thiophene

The amounts of tetrahydrothiophene and octane have been determined in the hydrodesulfurization product of thiophene on molybdenum catalysts under various conditions. The results are interpreted as evidence for a consecutive reaction mechanism consisting of ring hydrogenation followed by decomposition of the saturated sulfur compound.

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- . .

     

Comparison of the acid strength of solid catalysts

The catalytic activity of some solid acidic catalysts was tested in the depolymerization of paraldehyde. It was found that the activities of sulfonated ion exchange resin and mounted phosphotungstic acid strongly exceed the activity of silica-alumina and other oxide catalysts. By means of Brönsted relationship, the differences in H_O of the surfaces were estimated.

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. , - - . H_O .

     

Effect of preparation conditions on the properties of carbon-supported nickel catalysts

Carbon-supported Ni catalysts were prepared from nickel nitrate or chloride. Characterization was carried out by H₂ and CO chemisorption, XRD and TEM. Catalysts were further tested in the hydrogenolysis of n-butane.

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, , . H₂ CO, ., -.

     

Influence of the number of active sites on kinetic characteristics

The possibility for a complicated dependence of the steady-state reaction rate on the total number of catalyst active sites is shown for nonlinear mechanisms.

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.

     

A method for the treatment of experimental data. Kinetic system comprising two irreversible first order consecutive reactions

A method is proposed for the treatment of data from a kinetic system comprising two irreversible first order consecutive reactions (ABC). It is based on the solving of contrary propositions for an ordinary differential equation.

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(ABC). .