Deoxypegan-1-one derivatives. synthesis and borohydride reduction of 3-[(E)-arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolin-1(2H)-ones

3-[(E)-Arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolin-1(2H)-ones were prepared by reaction of quinazolyl-2-propionic acid hydrochloride with aromatic aldehydes in acetic anhydride in the presence of Et₃N. 3-[(E)-Arylmethylidene]-1,2,3,9-tetrahydropyrrolo[2,1-b]quinazolin-1-ols were formed by reduction of the 3-arylidene derivatives with sodium borohydride in methanol, readily lost water when heated with acids, and were converted into 3-[(E)-arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolines. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 463–467, September–October, 2006.     

Modular design of icosahedral metal clusters

The concept of crystalline module, that is, an unambiguously isolated, repeated quasi-molecular element, is introduced. This concept is more general than the concept of crystal lattice. The generalized modular approach allows extension of the methods and principles of crystallography to quasi-crystals, clusters, amorphous solids, and periodic biological structures. Principles of construction of aperiodic, nonequilibrium regular modular structures are formulated. Limitations on the size of icosahedral clusters are due to the presence of spherical shells with non-Euclidean tetrahedral tiling in their structure. A parametric relationship between the structures of icosahedral fullerenes and metal clusters of the Chini series was found.     

Cathodic reduction of SO2 in the presence of organic dihalides

The reaction of the electrolytically generated SO ₂ ^– anion radical with 1,-dihalides is used for the synthesis of sulfur containing heterocycles like oxathiolane-, oxathiane-, thiane- and thiepane-oxides. 1,2-Dihalides are reductively deblocked to give olefines.

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Kathodische Reduktion von SO₂ in Gegenwart organischer Dihalogenide

Zusammenfassung Die Reaktion des elektrolytisch erzeugten SO ₂ ^– -Anionradikals mit 1,-Dihalogeniden führt zu schwefelhaltigen Heterocyclen wie Oxathiolan-, Oxathian-, Thian- und Thiepanoxiden. 1,2-Dihalogenide geben durch reduktive Eliminierung Olefine.

     

Electrocatalytic dehalogenation of α-bromoketones in the presence of Cp2TiCl2

Processes of direct and electrocatalytic (in the presence of electrochemically reduced Cp₂TiCl₂) reduction of three α-bromoketones containing the C(sp³)-Br or C(sp²)-Br bond, viz., 2-bromo-and 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-ones and α-bromo-acetophenone, were studied by cyclic voltammetry and preparative electrolysis. In all cases, the dissociative electron transfer proceeds via the concerted mechanism. Preparative electrolysis of these α-bromoketones in the presence of Cp₂TiCl₂ affords the reductive debromination products in 40–80% yield at low cathodic potentials (−0.85 V vs. Ag/AgCl/KCl). In the case of 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-one in the potentiostatic regime, only one bromine atom can be eliminated selectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 977–983, May, 2007.     

Pheromone, 3.Mitt.: Eine einfache Methode zur Steuerung der Reduktion von α-Alkoxy-carbonylverbindungen

Summary Enantiomerically pure 1,2-diols bearing optionallysyn oranti configurated secondary hydroxylic groups are synthesized from acetal-protected cyanohydrins. After resolution of the diastereomers the cyanohydrins are converted into -alkoxy-ketones by Grignard-reaction followed by reduction using common chelating or non-chelating agents. Among others syntheses of enantiomerically pure pheromones,endo-Brevicomin,exo-Brevicomin and Dispalure are given as examples.

Prof. Dr. Hans Berbalk zum 70. Geburtstag gewidmet     

Comparative analysis of affine scaling algorithms based on simplifying assumptions

We analyze several affine potential reduction algorithms for linear programming based on simplifying assumptions. We show that, under a strong probabilistic assumption regarding the distribution of the data in an iteration, the decrease in the primal potential function will be with high probability, compared to the guaranteed(1). ( 2n is a parameter in the potential function andn is the number of variables.) Under the same assumption, we further show that the objective reduction rate of Dikin's affine scaling algorithm is with high probability, compared to no guaranteed convergence rate.Research supported in part by NSF Grant DDM-8922636.     

Enhancement of the solubilities of polycyclic aromatic hydrocarbons by weak hydrogen bonds with water

Summary The thermodynamics of mobile order is applied to predict the aqueous solubility of liquid and solid aliphatic and polycyclic aromatic hydrocarbons. The solubility values are mainly determined by the magnitude of the hydrophobic effect. However, contrary to the solubilities of the alkanes, the solubilities of polycyclic aromatic hydrocarbons in water predicted in absence of solute-solvent hydrogen (H) bonds are systematically too low. This shows the contribution of weak specific interactions between the OH groups and the electrons of the aromatic substances. According to the theory, these interactions are characterized by a stability bility constant K_o which can be derived from solubility data. At 25°C, this constant amounts to 80 cm³/mol, the order of magnitude of which can be explained by the competition of these intermolecular bonds with the rather weak self-association bonds in the secondary chains of water.     

Effect of film thickness on the electro-reduction of molecular oxygen on electropolymerized cobalt tetra-aminophthalocyanine films

We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O₂) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O₂ reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O₂ to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy.     

(R)-2,3-Cyclohexylideneglyceraldehyde, a novel template for facile and simple entry into chiral hydroxy γ-lactones: synthesis of (−)-muricatacin

(R)-2,3-Cyclohexylideneglyceraldehyde 1 has been used in a simple and efficient synthesis of (−)-muricatacin 10. The required chiron, syn-alkanetriol 2a was prepared by the reduction of a ketone 3 derived from 1.     

Electrochemical Reduction of Monochlorinated Hydrocarbons at a Hydrophobic Zn/PTFE Composite‐Electroplated Zn Electrode in a Water‐Acetonitrile Mixture

Composite‐electroplating of zinc particles with polytetrafluoroethylene at a zinc substrate resulted in a working electrode which could be used at high negative potentials (to ?2.5 V vs. Ag/AgCl) without significant hydrogen evolution. The electrodes were characterized by SEM and CV and were used to detect organochloride compounds in a water‐acetonitrile mixture, by potential step methods.