Researches on benzodiazines

2-R-Quinazolones have been synthesized (R=Me, Ph,-pyridyl,-furyl), and subsequently the 4-chlorides and the corresponding 2-R-4-hydrazinoquinazolines were obtained. By the reaction of orthoformic ester and nitric acid on the hydrazines, 5-R- [3, 4-c]-s-triazoloquinazolines and 5-R- [1, 5-c] tetrazoloquinazolines were prepared, respectively. The compounds in which R=Me differ considerably from compounds with other groups, both in color and stability of intermediate reaction products. 5-R- [1, 5-c] tetrazoloquinazolines are hydrolyzed by HCl into quinazol-4-ones.For Part IV see [1].     

The use of Hückel theory charge densities and localization energies for the prediction of kinetic and thermodynamic factors involved in an assumed model for the hydrohalogenation of 1,3-butadiene,isoprene and chloroprene

It is assumed that the first step in the hydrohalogenation of a diene under conditions such that an ionic mechanism is operative involves the formation of a linear carbonium ion via attachment of a proton to the 1-position and that the second step involves addition of the halide ion to either the 2- or 4-positions. If it is also assumed that hyperconjugation plays some non-negligible role in the carbonium ion intermediate, then it turns out that the use of Hückel theory charge densities and localization energies predict (1) that the 1,2-product is kinetically favored in the cases of butadiene and isoprene, (2) that the 1,4-product is kinetically favored in the case of chloroprene, and (3) that the 1,4-product is thermodynamically favored in all of the above systems. All of these predictions appear to be in agreement with available experimental results.

---

Zusammenfassung Bei der Addition von Halogenwasserstoffen an die hier untersuchten Diene wird im Reaktions-ablauf ein lineares Carbeniumion angenommen. Das Proton wird in 1-Stellung addiert und in einem zweiten Schritt wird das Halogenion in 2- oder 4-Stellung angelagert. Weiter wird angenommen, daß Hyperkonjugation beim intermediären Carbeniumion eine Rolle spielt. Aus den mit der Hückel-theorie ermittelten Ladungsverteilungen und Lokalisierungsenergien läßt sich dann voraussagen, daß (1) das 1,2-Produkt bei Butadien und Isopren, (2) das 1,4-Produkt bei Chloropren kinetisch und (3) das 1,4-Produkt in allen Fällen thermodynamisch bevorzugt ist. Diese Voraussagen scheinen mit den bekannten experimentellen Resultaten übereinzustimmen.

---

Résumé On admet que l'hydrohalogénation d'un diène dans des conditions où prévaut un mécanisme ionique comporte comme première étape la formation d'un ion carbonium linéaire par addition d'un proton à la position 1 et comme seconde étape l'addition de l'ion halogène à l'une des positions 2 ou 4. Si l'on admet par ailleurs que l'hyperconjuguaison joue un rôle non négligeable dans l'intermédiaire carbonium, l'emploi de la théorie de Hückel permet de prédire à l'aide des densités de charge et des énergies de localisation (1) que le produit 1,2 est favorable du point de vue cinétique dans les cas du butadiène et de l'isoprène (2) que le produit 1,4 est favorable du point de vue cinétique dans le cas du chloroprène et (3) que le produit 1,4 est favorable du point de vue thermodynamique dans tous ces systèmes. Toutes ces prédictions sont apparemment en accord avec les résultats expérimentaux disponibles.

     

Vinylacetylene chemistry

It is shown that heating vinylacetylenic piperidols I with phosphorus oxychloride in pyridine solution gives dienynes II, the structure of which is determined, in the case of II (R=H), by means of IR spectra and PMR. Hydration of the dienynes II (R=H, Me) in the presence of mercuric sulfate in methanol solution gives -methoxyketones III (R=H, Me). It is also shown that III and aqueous solutions of ammonia or primary amines give the bicyclic piperid-4-ones IV. In the synthesis of IV (R=H, R₁ = i-Pr, Bu) imines V are obtained, which on hydrolysis give piperidones IV (R = H, R₁ = i-Pr, Bu). When the ß-methoxyketone III (R = H) is heated with 5% sulfuric acid in the presence of mercuric sulfate, chroman-4-one is formed.     

Magnetic properties of copper(II) complexes with some hydrazones of substituted salicylaldehydes

A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H₂L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO₄)(CH₃OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment.     

Codigestion of manure and organic wastes in centralized biogas plants: status and future trends

Centralized biogas plants in Denmark codigest mainly manure, together with other organic waste such as industrial organic waste, source sorted household waste, and sewage sludge. Today 22 large-scale centralized biogas plants are in operation in Denmark, and in 2001 they treated approx 1.2 million tons of manure as well as approx 300,000 of organic industrial waste. Besides the centralized biogas plants there are a large number of smaller farm-scale plants. The long-term energy plan objective is a 10-fold increase of the 1998 level of biogas production by the year 2020. This will help to achieve a target of 12-14% of the national energy consumption being provided by renewable energy by the year 2005 and 33% by the year 2030. A major part of this increase is expected to come from new centralized biogas plants. The annual potential for biogas production from biomass resources available in Denmark is estimated to be approx 30 Peta Joule (PJ). Manure comprises about 80% of this potential. Special emphasis has been paid to establishing good sanitation and pathogen reduction of the digested material, to avoid risk of spreading pathogens when applying the digested manure as fertilizer to agricultural soils.     

A new method for the synthesis of CF3-containing aminovinyl ketones

A new method for the synthesis of aminovinyl trifluoromethyl ketones was developed. The method is based on the reactions of 4-sulfonyl-1,1,1-trifluorobut-3-ene-2,2-diols with various alkyl-, aryl-, dialkyl-, and alkylarylamines. The stereochemistry of the compounds obtained was studied.     

Determination of equilibrium constants of alkaline earth metal ion chelates with Dowex A-1 chelating resin

A complexation chemistry model is applied to chelating ion-exchange systems and a method is presented for the determination of equilibrium constants for metal ion chelates with these resins. Protonation constants for the iminodiacetic based chelating resin Dowex A-1 were determined from potentiometric pH-data. Equilibrium constants were determined for 1:1 beryllium, magnesium, calcium, strontium and barium chelates with the resin in a wide pH range by measuring the concentrations of respective metal ions in the aqueous phase with direct current plasma atomic emission spectrometry (DCP-AES). A batch technique was used for the equilibrium experiments. At pH below 7 protonated 1:1 species were also found to be formed with the resin. From the obtained equilibrium constants, theoretical distribution coefficients were calculated as function of pH for respective metal ion resin system.     

Dynamics of caged ions in glassy ionic conductors

At sufficiently high frequency and low temperature, the dielectric responses of glassy, crystalline, and molten ionic conductors all invariably exhibit nearly constant loss. This ubiquitous characteristic occurs in the short-time regime when the ions are still caged, indicating that it could be a determining factor of the mobility of the ions in conduction at longer times. An improved understanding of its origin should benefit the research of ion conducting materials for portable energy source as well as the resolution of the fundamental problem of the dynamics of ions. We perform molecular dynamics simulations of glassy lithium metasilicate (Li2SiO3) and find that the length scales of the caged Li+ ions motions are distributed according to a Levy distribution that has a long tail. These results suggest that the nearly constant loss originates from "dynamic anharmonicity" experienced by the moving but caged Li+ ions and provided by the surrounding matrix atoms executing correlated movements. The results pave the way for rigorous treatments of caged ion dynamics by nonlinear Hamiltonian dynamics.