Palladium-assisted multicomponent synthesis of 2-aryl-4-aminoquinolines and 2-aryl-4-amino[1,8]naphthyridines

A palladium-mediated multicomponent domino reaction leading to 2-aryl-4-amino-quinolines and 2-aryl-4-amino[1,8]naphthyridines is reported. The scope of the reaction was examined using carbon monoxide, two 2-ethynyl-arylamines, four aryl iodides, and 10 primary amines as substrates. The selection of the appropriate catalytic system was achieved testing several palladium/phosphine systems and overrides previously reported drawbacks associated with the use of primary amines in related reactions. Moreover several features concerning the role of both palladium [(0) and (II)] and phosphines are reported.     

Simultaneous C-H-N and S microdetermination by combustion and gas chromatography

Summary A method based on flash-combustion of the sample in a flow of temporarely oxygen-enriched helium, catalytic oxidation and reduction of the combustion gases within the same reactor, gas-chrom- matographic separation and thermal-conductivity detection of the end-products, has been developed in order to determine C-H-N-S simultaneously in organic and inorganic substances, with a 0.1–2 mg sample. To develop this method, optimization of analytical parameters was necessary because of the chemical and physical behaviour of oxides of sulphur in the analyser. Therefore flashcombustion in a tin container, use of a tungstic oxide oxidative layer close to a copper reductive layer, setting the copper temperature at 850° C and selective halogen adsorption are the main features. The temperature of 850° C for the copper gives a quantitative yield of SO₂ in spite of the reaction between sulphur oxides and cupric oxide, and also gives quantitative reduction of the nitrogen oxides. The individual components of the combustion mixture are separated by means of a Porapak QS column and detected in the sequence Na, CO₂, H₂O and SO₂, the signals being automatically integrated and printed. Detector response for SO₂ is linear from someg up to 10 mg.

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Zusammenfassung Zur gleichzeitigen Bestimmung von C, H, N und S in 0,1 bis 2 mg anorganischer oder organischer Substanz wurde ein Verfahren entwickelt, wobei die Substanz in zeitweilig sauerstoff-angereichertem Helium verbrannt, die Verbrennungsprodukte im selben Reaktionsrohr zunächst katalytisch oxydiert, dann reduziert werden. Anschließend werden die Endprodukte gas-chromatographisch getrennt und mittels Wärmeleitfähigkeitsmessung bestimmt. Zur Entwicklung dieses Verfahrens mußten die analytischen Parameter wegen des chemischen und physikalischen Verhaltens der Schwefeloxide optimiert werden. Daher werden Flammenverbrennung in einem Zinngefäß, Verwendung von Wolframoxid als oxydierende Schicht unmittelbar neben Kupfer als reduzierender Schicht, die auf 850° C gehalten wird, sowie selektive Adsorption der Halogene als wichtigste Schritte betrachtet. Die Temperatur von 850° C gewährleistet quantitative Ausbeute an SO₂ im Gegensatz zur Reaktion zwischen Schwefeloxiden und Kupferoxid und führt auch zur quantitativen Reduktion der Stickstoffoxide. Die einzelnen Teile des Verbrennungsgemisches werden mit einer Säule aus Porapak QS getrennt und in der Reihenfolge N₂, CO₂, H₂O und SO₂ nachgewiesen, wobei die Signale automatisch integriert und gedruckt werden. Der Detektorausschlag für SO₂ ist von einigen Mikrogramm bis 10 mg linear.

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Dedicated to Prof. H. Lieb for his 90th birthday.

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Presented at the International Symposium on Microchemical Techniques, May 23–27, 1977, Davos, Switzerland.     

Transfer reaction and molecular weight distribution in the anionic polymerization of formaldehyde

The anhydrous formaldehyde polymerization is examined. The influence of initiator and monomer concentration on the molecular weight and molecular weight distribution are emphasized. A mechanism for the transfer to the monomer is introduced. This mechanism is confirmed by experimental results and leads to the formation of formyl end groups. The influence of various initiators on the transfer reaction also is evaluated.     

Molecular complexes of hydrazides with copper(II)

Summary The reaction of substituted hydrazides with copper(II) chloride was investigated in the solid state or in solution in order to account for substituent effects. Spectroscopic results and values of the formation constants indicate the occurrence of strong complexes.

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Molekulare Komplexe von Hydraziden mit Kupfer(II)

Zusammenfassung Die Reaktionen von substituierten Hydraziden mit Kupfer(II)chlorid wurden im Festzustand und in Lösung untersucht. Die spektroskopischen Ergebnisse und die Werte der Bildungskonstanten zeigen die Koordinierung zu starken Komplexen an.

     

Study of carbon,hydrogen and nitrogen determination by combustion-gas chromatography

Summary The method for carbon-hydrogen-nitrogen determination based on dynamic rapid combustion of the sample, gas chromatographic separation and thermal-conductivity measurement of the gases N₂, CO₂ and H₂O is critically considered and improved. In order to achieve instantaneous combustion of all types of organic compounds, oxidizable metallic containers are used for the sample and dropped in the hot combustion zone while the carrier gas is momentarily enriched with pure oxygen. Flash combustion of the sample is followed by catalytic oxidation on a newly developed active catalyst. This reagent, adsorption-free and thermally resistent, consists of pure chromic oxide, mechanically compressed and granulated. Copper treated with silver is used as reducing reagent. Unwanted gases are eliminated with Co₃O₄ containing silver, and by utilizing the chemiadsorption properties of the column packing. Measurements are made by integrating and printing the electrical signal. The analytical process is controlled by means of a potentiometric recorder. The increased combustion capacity, the practical absence of blanks and the very extended linearity of response of the detector make possible CHN determination in sample sizes of 0.1–3 mg. Except for sample weighing and calculation of results from the printed integration values, all the operations are automatically controlled by a preset programme.

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Zusammenfassung Das Verfahren zur Bestimmung von C, H und N, das auf der dynamischen Schnellverbrennung der Probe, der gaschromatographischen Trennung und Wärmeleitfähigkeitsmessung der Gase N₂, CO₂ und H₂O beruht, wurde kritisch überdacht und verbessert. Um die sofortige Verbrennung aller Arten organischer Verbindungen zu erzielen, wurden die in oxydierbaren Metallbehältern eingewogenen Proben in die heiße Zone des Verbrennungsrohres eingeführt, während gleichzeitig das Transportgas kurzfristig mit Sauerstoff angereichert wurde. Die Verbrennung erfolgt durch katalytische Oxydation an einem neu entwickelten Kontakt, der nicht adsorbiert, hitzebeständig ist und aus reinem, gepreßtem und gekörntem Chromoxid besteht. Versilbertes Kupfer dient als Reduktionsmittel. Störende Gase werden mit silberhältigem Co₃O₄ sowie durch Chemisorption an der Säulenfüllung entfernt. Die elektrischen Signale werden integriert und ausgedruckt. Der ganze analytische Vorgang wird durch einen Spannungsschreiber kontrolliert. Die erhöhte Verbrennungskapazität, das praktisch vollständige Fehlen eines Blindwertes sowie die weitgehende Linearität der Detektoranzeige erlauben CHN-Bestimmungen in nur 0,1 bis 3 mg Probe. Abgesehen von der Einwaage und der Berechnung der Resultate aus den ausgedruckten Werten verlaufen alle Vorgänge automatisch und programmiert.

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Dedicated to the memory of Dr. Wolfgang Schöniger.     

The determination of oxygen in brass and zinc by a vacuum carbon-reduction techniques

A vacuum carbon-reduction technique for the determination of oxygen in brass and zinc has been studied. As a preliminary, zinc is removed from the samples, sealed in predegassed graphite capsules, in a silica furnace maintained at ca. 850°C under vacuum in a vacuum fusion instrument. The residual contents of the capsules are then analysed in sequence at 1450°C in the main furnace of the apparatus, to which they are transferred without breaking the vacuum. The procedure developed affords a detection limit of 0.5–1 ppm of oxygen for samples weighing ca. 1.5 g.     

Contribution of mass spectrometric techniques to the structure elucidation of antibiotic GE2270A,a novel inhibitor of bacterial protein synthesis

GE2270A is a novel antibiotic active against Gram-positive bacteria and anaerobes. Its structure originates from a peptidic backbone, the amino acids of which have been modified to produce a macrocycle and a side-chain. It contains a heterocyclic chrornophonc system, a number of thiazoleamino acids and three unmodified natural amino acids. The structure [relative molecular mass (RMM) 1289] was determined using various spectroscopic techniques, of which fast atom bombardment mess spectrometry, gas chromatography/mass spectrometry, desorption chemical ionization mass spectrometry and fast atom bombardment tandem mass spectrometry played an important role. The mass spectrometric approach was applied to the intact molecule and to the various hydrolysis products, including the chromophoric part (RMM 634).     

Determination of triacylglycerols in donkey milk by using high performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry

The separation and determination of triacylglycerols (TAGs), which are the main components of naturally occurring fats and oils, in milk fat is a challenging task due to the very complex nature of this matrix. In the present study the TAG fraction of donkey milk lipids has been characterized by using high performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS). HPLC in reversed phase mode has been used for TAG separation and silver ion (Ag+) HPLC has been used as a second dimension to clarify and confirm the identification. The RP-HPLC eluate was fractionated and the fractions of interest were injected onto the Ag+-HPLC column. In both cases peak assignment was carried out by combining retention data with APCI-MS spectra information. In total, 55 TAGs in donkey milk fat were identified (without considering the positional isomers) and quantified on the basis of percentage peak areas in the RP-HPLC chromatogram (without the use of correction factors). Amongst the identified triacylglycerols, POLn, POO, PPO, CaPO, POL, and PPoO proved to be the main components of the TAG fraction of donkey milk.     

Remote control of enzyme selectivity: the case of stevioside and steviolbioside

The remote control of lipase PS site- and regioselectivity by substrate modification has been observed in the acetylation of stevioside (1) and steviolbioside (2): deglucosylation at position C-19 changed the acylation site of the sophorose moiety linked at C-13. In fact, while esterification of 1 gave mainly the corresponding 6″-O-acetylated derivative, acylation of 2 gave exclusively the 6′-O-monoester. A possible rationale has been suggested, based on the conformational behavior of the substrates in different simulated solvents.     

Lower semicontinuous perturbations of maximal monotone differential inclusions

We prove existence of solutions to 1 $$\dot x \in - Ax + F\left( {t,x} \right),x\left( a \right) = x^0 ,$$ whereA is a maximal monotone operator inR ⁿ andF is a multifunction measurable in (t, x) and l.s.c. inx, satisfying a sublinear growth condition.