Application of the ring oven method to the determination of dyestuffs

Summary The Weisz ring oven method has been applied to the semiquantitative determination of indigo carmine, erythrosin A, amaranth O, new coccine, Victoria blau B, tartrazine, azorubin S, alizarin S, eosin, light green SF, Guinea green B, fuchsin, eriochrome black T, saphranine, ponceau 3 R, cyanine, gelborange S, and methyl violet 6 B. The amount of dye needed ranges from 0.5 to 20g, and the error is generally less than 5%. The method has been used for the determination of azorubin S, methyl violet 6 B, tartrazine, and amaranth O in various materials.

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Zusammenfassung Die Ringofenmethode vonWeisz wurde für die semiquantitative Bestimmung folgender Farbstoffe angewendet: Indigocarmin, Erythrosin A, Amaranth O, Neucoccin, Viktoria blau B, Tartrazin, Azorubin S, Alizarin S, Eosin, Lichtgrün SF, Guineagrün B, Fuchsin, Eriochromschwarz T, Saphranin, Ponceau 3 R, Cyanin, Gelborange S und Methylviolett 6 B. Die dazu nötige Farbstoffmenge beträgt 0,5 bis 20g, der Fehler ist im allgemeinen geringer als 5%. Die Methode wurde für die Bestimmung von Azorubin S, Methylviolett 6 B, Tartrazin und Amaranth O in verschiedenen Materialien angewendet.

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Résumé On a appliqué la méthode du four annulaire deWeisz au dosage semi-quantitatif du carmin d'indigo, de l'érythrosine A, de l'amaranthe O, de la coccine nouvelle, du bleu Victoria B, de la tartrazine, de l'azorubine S, de l'alizarine S, de l'éosine, du vert lumière SF, du vert Guinée B, de la fuchsine, du noir ériochrome T, de la safranine, du ponceau 3 R, de l'orangé jaune, de la cyanine S et du violet de méthyle 6 B. La quantité de colorant nécessaire va de 0,5 à 20g et l'erreur est généralement inférieure à 5%. On a appliqué la méthode au dosage de l'azorubine S, du violet de méthyle 6 B, de la tartrazine et de l'amaranthe O dans diverses substances.

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We wish to thank Mrs.Lidija Pfendt of the Faculty of Sciences in the University of Belgrade for doing the spectrophotometric analyses.     

Total luminescence of organic molecules of petrochemical interest : Naphthalene,phenanthrene and 1,2,4,5-tetramethylbenzene

Total emission, phosphoroscopically resolved emission, excitation and mean lifetime in the excited triplet state were measured for three organic molecules of petrochemical interest in EPA rigid glass at 77° K. Fluorescence was also measured at room temperature in n-heptane. Methods for the determination of these three molecules in individual solutions are presented and compared with known methods by absorption spectroscopy. An attempt was made to quantify a blend of the three components by luminescence techniques.     

Total synthesis of the marine alkaloid (-)-lepadin B

An enantioselective total synthesis of (-)-lepadin B has been developed starting from (2S,4S)-2,4-O-benzylidene-2, 4-dihydroxybutanal. The key steps in the synthesis include the use of an aqueous intramolecular acylnitroso Diels-Alder reaction to afford the trans-1,2-oxazinolactam and Suzuki cross-coupling reaction to elaborate the (E,E)-octadienyl unit.     

Reactions of 1-Allenylpyrazole and 1-Allenyl-1,2,4-triazole with Hydrogen Chloride and Metal Chlorides

1-Allenylpyrazole and 1-allenyl-1,2,4-triazole react with hydrogen chloride via proton addition at the pyridine-like nitrogen atom (N² and N⁴, respectively). In the reaction with 1-allenylpyrazole, 1-[(E)-3-chloro-1-propenyl]pyrazole is also formed via regio- and stereoselective addition of hydrogen chloride to the propadienyl group. 1-Allenylpyrazole and 1-allenyl-1,2,4-triazole act as unidentate ligands with respect to Co, Ni, Cu, Zn, Cd, Pd, and Sn, the donor centers being N² and N⁴, respectively. Apart from mononuclear coordination compounds, 1-allenylpyrazole gives rise to polymeric complexes which contain units and blocks formed by the free ligand.     

Atomic spectroscopy for detection in thermal analysis

An atomic absorption spectrophotometer is coupled to a conventional thermoanalytical quartz furnace as used for TG and DTG to detect the thermally evolved products. In this combined system, the dry aerosol (smoke) obtained by cooling the vapour evolved is transported from the furnace to the flame for metal-specific atomic absorption detection. The particular design of the furnace outlet promotes the formation of stable aerosols. Optimum experimental conditions were determined, using zinc chloride solution, by varying the specimen mass, the heating rate and the flow rate of the furnace gas at a linear temperature program. The absorbancevs. temperature curves obtained with this method for various zinc compounds are compared with the corresponding DTG curves. The applicability of the technique for studying heterogeneous reactions with carbon tetrachloride and hexane vapours is presented. The utilization of an atomic absorption spectrophotometer equipped with a quartz cuvette for detecting the thermal evolution of mercury vapours is described, as well as detection potentials by molecular absorption (for NO and NH₃) and light scattering (for smoke evolved from organic matter). The results obtained with the suggested methods may, in some respects, valuably complement the results achieved with DTG and with flame ionization detection.

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Zusammenfassung Ein Atomabsorptionsspektrometer wurde mit einem konventionellen thermoanalytischen Quarzofen gekoppelt um thermische Abspaltprodukte nachzuweisen. In diesem kombinierten System wird das durch Kühlung des entwickelten Dampfes erhaltene Aerosol (Rauch) vom Ofen in die Flamme für den metallspezifischen Atomabsorptionsnachweis übergeleitet. Die spezielle Ausbildung der Austrittsöffnung gewährleistet die Bildung eines stabilen Aerosols. Die optimalen Versuchsbedingungen wurden durch Zinkchloridlösungen bei Anderung der Probenmasse, der Aufheizgeschwindigkeit und der Strömungsgeschwindigkeit des Ofengases im linearen Temperaturprogramm ermittelt. Die mit dieser Methode für verschiedene Zinkverbindungen erhaltenen Absorptions—Temperatur-Kurven wurden mit den entsprechenden DTG-Kurven verglichen. Die Anwendbarkeit dieser Technik bei dem Studium heterogener Reaktionen mit Kohlenstofftetrachlorid und Hexandämpfen wird gezeigt. Der Einsatz eines mit einer Quarzküvette zum Nachweis der thermischen Entwicklung von Quecksilberdampf versehenen Atomabsorptionsspektrometers wird beschrieben, sowie die Nachweisgrenze durch molekulare Absorption (für NO und NH₃) und Lichtstreuung (für aus organischem Material entwickelten Rauch). Die bei den beschriebenen Methoden erhaltenen Ergebnisse können, in mancher Hinsicht, die durch DTG und Flammenionisationsnachweis erhaltenen Ergebnisse wertvoll ergänzen.

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- , , . (), , . . , . — , , -. . - , , , ( NO NH₃) ( , ). , , , - .

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Presented in part at the 24th Hungarian Conference on Analytical Sptecroscopy, Miskolc, June 15–18, 1981. Abstracts pp. 159–162.

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The authors wish to express their thanks to S. Gál for his assistance in the present application of the temperature programmer developed by him and his group, and for the valuable discussions on the subject. Thanks are also due to K. Tomor and J. Kmives who participated in the comparative thermoanalytical measurements and their analysis.     

Investigation of transitions and relaxation processes in polystyrene by using positron annihilation

The glass transition and relaxation processes in polystyrene resins with the number average molecular weight ranging from 7.0·10² to 9.8·10⁴ were studied with the positron annihilation technique. The pick-off annihilation lifetime of ortho-positronium (₃) and its intensity (I ₃) were measured in the temperature range from 20 to 430 K. The glass transition temperature (T _g) was determined as an onset temperature coefficient of ₃.T _g shows the molecular weight dependence in these samples. BelowT _g, local motions were detected by measurements ofI ₃. The local motions could be observed above 100 K in this experiment.I ₃ show the minimum at around 250 K and it does not show molecular weight dependence.     

Thermogravimetry and differential scanning calorimetry of natural and synthetic melanins

The thermal stability of natural melanins from bovine eyes, black human hair and the hard core of banana peel, synthetic melanins obtained enzymatically or by autoxidation of various precursors, and chemically modified synthetic melanins was studied by DSC and TG analysis. It was shown that the resistance of melanins to thermal degradation depends on their origin. Synthetic melanins were found to be more stable to thermal decomposition than natural melanins. Methylation of melanins caused a significant increase in thermal stability. The DSC curves of melanins reveal typical relaxation phenomena in the temperature range 293–413 K.

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Zusammenfassung Mittels DSC und TG wurde die thermische Stabilität von natürlichen Melaninen aus Rindsaugen, aus schwarzem menschlichen Haar und aus Hartteilen von Bananenschalen, weiterhin von enzymatisch oder durch Autoxidation aus verschiedenen Präkursoren synthetisierten Melaninen sowie von chemisch modifizierten synthetischen Melaninen untersucht. Es zeigte sich, daß die Beständigkeit von Melaninen gegenüber thermischem Abbau von ihrem Ursprung abhängt. Synthetische Melanine erwiesen sich in der thermischen Zersetzung als stabiler als Melanine natürlichen Ursprunges. Durch Methylierung wird eine eindeutige Steigerung der thermischen Stabilität verursacht. Im Temperaturbereich 293–413 K zeigen weisen die DSC-Kurven der Melanine typische Relaxationserscheinungen auf.

     

Expanded scope in ethylene-alkyne cross-metathesis: coordinating heteroatom functionality at the propargylic position

The Grubbs 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene-substituted ruthenium complex 1 catalyzed ethylene-alkyne cross-metathesis and was shown to tolerate free hydroxyl groups and coordinating functionality at the propargylic and homopropargylic positions. Hindered and enantiomerically enriched 1-substituted alkynes also react efficiently under the reported conditions.     

Benzindoles. 23. 2-formyl- and 3-formyl-4,5-benzindoles

It is shown that, in addition to the usually formed 3-formyl-4,5-benzindole, 2-formyl-4,5-benzindole can be obtained via the Vilsmeier reaction. The IR, PMR, and UV spectra of the 2- and 3-formyl isomers are compared, and their possible conformations are discussed.See [1] for Communication 22.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1984.     

Preparation,and infrared and thermal properties of six adducts of tetrakis-(8-hydroxyquinolinato)thorium(IV)

Six adducts of the tctrakis(8-hydroxyquinolinato) complex of thorium(IV) with 8-hydroxyquinoline, pyridine, urea, dimethylsulphoxide, dimethylformamide and 1,10-phenanthroline were prepared and characterized, the infrared bands for the room-temperature forms are given and their particular thermal properties are reported. The thermal analyses were performed mostly in the presence of air, but in some cases an argon atmosphere was used for comparison. The adducts were lost from the principal complex at temperatures varying between 110 and 290°. Intermediate oxygenated complexes were formed in each case at about 400°. The thermal data suggest the standardization of a procedure for the formation of Th(C₉H₆NO)₄.

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Zusammenfassung Sechs Addukte des Tetrakis(8-hydroxyquinolinato)-Komplexes von Thorium(IV) mit 8-Hydroxyquinolin, Pyridin, Harnstoff, Dimethylsulphoxid, Dimethylformamid und 1,10-Phenanthrolin wurden dargestellt und charakterisiert. Infrarotbanden und spezielle thermische Eigenschaften der Raumtemperatur-Formen sind angegeben. Die thermischen Analysen wurden meist in Luft ausgeführt, in einigen Fällen zu Vergleichszwecken aber auch in Argonatmosphäre. Die Addukte wurden vom Komplex bei Temperaturen zwischen 110 und 290 °C abgegeben. Intermediäre oxydierte Komplexe wurden in jedem Fall bei etwa 400 °C gebildet. Die thermischen Daten ermöglichen die Standardisierung eines Verfahrens zur Darstellung von Th(C₉H₆NO)₄.

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-(8- ) (IV) 8- , , , - , 1,10-. - , . , , . 110–290°. 400° . Th(C₉H₆NO)₄.

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We are grateful to the Bangladesh University Grants Commission for a Fellowship Grant to AR.