Phthalocyanines and related compounds: XLII. Synthesis of phenyl-substituted tetraazachlorins and tetraazabacteriochlorins

New oxidation-resistant hexaphenyl-substituted tetramethyltetraazachlorin, its nickel complex, and tetraphenyl-substituted octamethyltetraazabacteriochlorin and octamethyltetraazaisobacteriochlorin nickel complexes were synthesized for the first time by mixed condensation of diphenylm aleonitrile with tetramethylsuccinonitrile in the presence of lithium dimethylaminoethoxide or nickel chloride. The products were characterized by electronic absorption, ¹H NMR, and mass spectra. Mixed condensation of diphenylsuccinonitrile with phthalonitrile in the presence of nickel chloride was found to give nickel complexes of phenylsubstituted benzo-fused tetraazaporphyrins rather than their hydrogenated derivatives.     

Oxidation of propene over various doped tungsten oxides

The oxidation of propene was studied on several tungsten oxides which contained small amounts of Ti, Ta, Nb and Sn. Only the Sn-containing specimen was found to be selective in the conversion of propene to acrolein. The catalytic results are correlated with crystal structures determined by electron microscopy.

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, Ti, Ta, Nb Sn. , , Sn, . , .

     

The di-π-methane rearrangement : The effect of 1,4-diene structure and conformation on the reaction efficiency and stereochemistry

The photochemistry of the stereoisomeric 1,3-dimethyl-3(2-phenylethenyl)cyclohexenes has been explored Direct irradiation of the cis- and trans-β-styrylcyclohexenes leads to di-π-methane rearrangement, producing the endo- and exo-3,7-dimethyl-8-phenybicyclo[5.1.0]oct-2-enes, and cis -trans isomerization, interconverting the 1,4-diene containing substrates. Triplet sensitized photolysis of both substituted cyclohexenes leads exclusively to cis-trans isomerization. Results from low conversion direct irradiations of the cis- and trans-β-styrylcyclohexenes indicate that the singlet rearrangements are stereospecific, and lead to formation of the 8-exo and 8-endo-phenylbicyclic octenes, respectively. The relationship between di-π-methane structure and triplet reaction efficiency, and the effect of conformation on the rearrangement stereochemistry are discussed.     

Extension of the separated pair theory

Assuming that the separated pair ground state wave function of a 2N-electron system is already known a method is given for constructing a suitable orthogonal complement to the set of product functions built up from strongly orthogonal geminals. All terms are explicitly given which may have nonzero matrix element with the separated pair ground state. Using perturbational techniques a second order correction is calculated. In the case of Be atom the magnitudes of contributions from terms omitted in the generalized separated pair theory are estimated and found to be appreciable.

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Zusammenfassung Unter der Annahme, daß der Grundzustand eines 2N-Elektronensystems in der Methode der getrennten Elektronenpaare bekannt ist, wird eine Methode angegeben, wie man den Basissatz von Produktfunktionen aus streng orthogonalen Geminalen geeignet vervollständigen kann. Alle mit dem Grundzustand kombinierenden Terme werden explizit angegeben. Mit Hilfe der Störungsrechnung wird eine Korrektur zweiter Ordnung berechnet. Im Falle des Be-Atoms wird die Größe der in der Theorie der getrennten Elektronenpaare vernachlässigten Beiträge abgeschätzt und als beträchtlich erwiesen.

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Résumé Si l'on suppose connue la fonction d'onde à paires séparées pour l'état fondamental d'un système à 2N électrons, une méthode décrite ici permet de construire convenablement un complément orthogonal à l'ensemble des fonctions produits de géminales fortement orthogonales. Tous les termes ayant un élément dematrice non nul avec l'état fondamental sont donnés explicitement. Une correction du second ordre est calculée au moyen des techniques de perturbation. Dans le cas de l'atome de beryllium, la grandeur des contributions des termes omis dans la théorie généralisée des pair es séparées est estimée et trouvée non négligeable.

     

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.     

Improvements to the distance geometry algorithm for conformational sampling of cyclic structures

Modifications to the distance geometry algorithm as embodied in the program DGEOM have been made to improve sampling capabilities. Specifically, torsion angle sampling replaces distance sampling for 1,4 atomic relationships and correlated distance sampling is disabled. The effects of these modifications are illustrated by comparing the different sets of conformations produced for butane. In addition, these changes are shown to increase the conformational sampling of two medium-sized rings, cycloheptadecane and caprylolactam. The current results for these molecules are compared to those of other conformational searching methods.     

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.     

Mass-spectrometric determination of metal chelates

Zusammenfassung Aus digitalisierten Raman- und Infrarotspekten von 70 Steroiden wurden die Summenspektren der Substanzen mit übereinstimmenden Strukturmerkmalen berechnet. In diesen Spektren sind Banden geringer Standardabweichung dann charakteristisch für ein Strukturmerkmal, wenn sie bei anderen Strukturmerkmalen fehlen. Sie sind dann für die Strukturaufklärung von Substanzen unbekannter Struktur geeignet.

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Raman spectroscopy and molecular structureIII. Selection of characteristic bands of polyatomic molecules by means of a computer

Digitized Raman and infrared spectra of 70 steroids are used for the calculation of summarized spectra of all substances with the same structural details. In these spectra bands with low standard deviation are characteristic for the structural detail if they are absent in the other groups of spectra. They can be used for the elucidation of unknown structures.

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Wir danken Herrn Dipl.-Phys. H. Barentzen für die Aufstellung des Computerprogramms sowie Frl. G. Pannek und Frau E. von Bühlow für die Hilfe bei der Verschlüsselung und Aufbereitung der Daten. — Der Deutschen Forschungsgemeinschaft und dem Landesamt für Forschung, Nordrhein-Westfalen, danken wir für Sachbeihilfen.