Theoretische Betrachtung der Diels-Alderschen Reaktion auf Grund der LCAO-MO-Theorie

Zusammenfassung Vorliegende Arbeit bietet eine theoretische Betrachtung derDiels-Alderschen Reaktion mit Hilfe der LCAO-MO-Methode in derHückelschen Näherung unter der grundsätzlichen Voraussetzung der dem aktiven Komplex vorausgehenden -Komplexbildung zwischen dem Dien und Dienophil. Die als Resultat der Wechselwirkung zwischen Dien und Dienophil auftretende, im Bereich des Energieminimums berechnete Delokalisationsenergie steht in linearer Korrelation zur Aktivierungsenergie.Am Beispiel der Wechselwirkung des Cyclopentadiens mit unterschiedlichen Dienophilen wird gezeigt, daß die Delokalisationsenergie inendo-Stellung des Diens und Dienophils stets kleiner ist als inexo-Stellung, was den Satz vonAlder erklärt.

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TheDiels-Alders reaction has been studied theoretically using the conventionalHückel LCAO-MO method. The investigation is based on regarding the formation of a -complex from the diene and dienophil as a forerunner of the transition state. A linear correlation exists between the energy of delocalization resulting from the diene—dienophil interaction and calculated for the region of the energy minimum and the energy of activation. The interaction of cyclopentadiene with various dienophils is used as an example showing that the delocalization energy of theendo situated diene and dienophil is always lower than the delocalization energy of theexo oriented ones, a fact that explainsAlders rule.

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Mit 5 Abbildungen     

The role of metallic palladium in the reductive decomposition of π-allyl palladium chloride in aqueous alkaline solutions

Russian Chemical Bulletin -     

Divinyl Sulfoxide: XI. Selective Addition of Carbonodithioate Anions to Divinyl Sulfoxide in the Water-Benzene System

Selective monoaddition of carbonodithioate anions to divinyl sulfoxide gives rise to O-alkyl S-[2-(vinylsulfinyl)ethyl] carbonodithioates [ROC(S)SK, R = Et, Bu; 42–50°C, 6 h, NaHCO₃, aqueous benzene].     

Bond additivity corrections for G3B3 and G3MP2B3 quantum chemistry methods

We have developed bond additivity correction (BAC) procedures for the G3-based quantum chemistry methods, G3B3 and G3MP2B3. We denote these procedures as BAC-G3B3 and BAC-G3MP2B3. We apply the procedures to compounds containing atoms from the first three rows of the periodic table including H, B, C, N, O, F, Al, Si, P, S, and Cl atoms. The BAC procedure applies atomic, molecular, and pairwise bond corrections to theoretical heats of formation of molecules. The BAC-G3B3 and BAC-G3MP2B3 procedures require parameters for each atom type but not for each bond type. These parameters have been obtained by minimizing the error between the BAC-G3B3 and BAC-G3MP2B3 predictions and the experimental heats of formation for a 155 molecule reference set, containing open and closed shell molecules representing various functional groups, multireference configurations, isomers, and degrees of saturation. As compared to former BAC-MP4, BAC-G2, and BAC-hybrid methods, BAC-G3B3 provides better agreement with experiment for a wider range of chemical moieties, including highly oxidized species involving SOx s, NOx s, POx s, and halogens. The BAC-G3B3 and BAC-G3MP2B3 procedures are applied to an extended test suite involving 273 compounds. We assess the overall quality of BAC-G3B3 with experiments and other theoretical approaches. For the reference set, the average error for the BAC-G3B3 results is 0.44 kcal/mol as compared to 0.82 kcal/mol for the raw G3B3. For the extended test set, the average error for the BAC-G3B3 results is 0.91 kcal/mol as compared to 1.38 kcal/mol for the raw G3B3. As compared to the other BAC procedures, the improved predictive capability of BAC-G3B3 and BAC-G3MP2B3 procedures is, to a large extent, due to the improved quality of G3-based methods resulting in much smaller BAC correction terms.     

Synthesis and electrochemical applications of fluorinated vinylazole copolymers for monitoring NO in model and biological systems

Copolymers of 1-vinyl-1,2,4-triazole and 5-vinyltetrazole with 1,1,5-trihydrooctafluoropentyl methacrylate and 1,1,7-trihydrododecafluoroheptyl methacrylate were prepared under the conditions of radical initiation. These copolymers were used for modification of the surface of a glassy carbon electrode, and the effect of the modification on the electrochemical behavior of the electrode in anodic oxidation of dopamine and NO was studied. The possibility of enhancing the selectivity of the electrochemical sensor for monitoring NO in biological media was demonstrated.     

Organoinorganic composites based on tetraethoxysilane and nitrogen polybases

Hybrid organoinorganic composites insoluble in water and organic solvents were prepared by the hydrolysis of tetraethoxysilane in the presence of poly-1-vinylpyrazole, poly-1-vinylimidazole, and poly-4-vinylpyridine. The composition of the composites was determined by the nature of the polymeric nitrogen base and hydrolysis conditions. The composites synthesized showed high sorption activity in the extraction of the [PdCl₄]^2?, [PtCl₆]^2?, and [AuCl₄]^? ions from hydrochloric acid solutions.     

Dehydrogenation of 1-(diphenylphosphinoyl)-2-(N′-phenylhydrazino)ethane and N-butyl-N′-phenylhydrazine

Dehydrogenation of 1-(diphenylphosphinoyl)-2-hydrazino-substituted ethanes and N-butyl-N′-phenylhydrazine to the corresponding hydrazone derivatives is performed. Both reactions were established to involve predominantly, if not exclusively, an azo intermediate.