Synthesis of azetidin-3-ones. Structure of N-tosyl-2-ethylazetidin-3-one

A one-step synthesis of azetidin-3-ones by intramolecular cyclization of 1-diazo-3-arenesulfamoylalkan-2-ones was developed. The yield of cyclic product increases to 70% in the presence of an alkyl or benzyl substituent in the hydrocarbon chain of the diazoketone. The structure of N-tosyl-2-ethylazetidin-3-one was studied by x-ray diffraction analysis and it was shown that the four-membered ring has 15 inflection.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 468–473, April, 1987.     

Grain Boundary Wetting in Polycrystals: 1. Probability of Wetting of Structural Elements

A model describing the wetting of structural elements in polycrystals such as grain boundaries (faces), triple lines (edges), and quaternary nodes (vertices) is proposed. It is assumed that the only driving force during wetting is the tendency of a system to the energy minimization due to the substitution of low-energy liquid–solid interfaces for high-energy grain boundaries. In this case, the anisotropy of grain boundary energy caused by the differences in misorientation of adjacent grains is taken into account, whereas the liquid–solid interface energy is assumed to be independent of the orientation. The well-known condition of grain boundary wetting (the Gibbs–Smith condition) is extended to the triple lines and quaternary nodes by introducing parameters determined as characteristic free energy of these elements.     

A study of the tautomerism of the N-alkyl-3-methoxycarbonyl-4-piperidinones and their hydrochlorides

The positions of the equilibria of N-alkyl-3-methoxycarbonyl-4-piperidinones in the liquid state, in water, in alcohols, and in CCl₄ have been determined by IR and UV spectroscopy. It has been shown that Meyer's equation is not satisfied for them. This is due to the high steric requirements of the solvating electron pair of the nitrogen atom. On the basis of the fact that on passing from the methyl ester of cyclohexan-1-one-2-carboxylic acid to the N-alkyl-3-methoxycarbonyl-4-piperidones the position of the equilibrium in the liquid state and in CCl₄ does not shift in the direction of the enol it is deduced that the spatial requirements of the free electron pair of the nitrogen atom do not appreciably exceed the steric requirements of the hydrogen atom. The IR and UV spectra of the chlorides of the N-alkyl-3-methoxycarbonyl-4-piperidinones in the solid state and in water and in alcohols are given.     

Beitrag zur Kenntnis der Pt(II)-Verbindungen mit Acetoxim

Zusammenfassung Es wurde die thermische Zersetzung dercis-undtrans-Isomeren des [PtAox ₂Cl₂] sowie des [PtAox ₃Cl]Cl mit Hilfe derTG-undTD-Kurven im Falle des reinen Komplexes sowie im Falle einer Mischung mit Al₂O₃ (1:3) geklärt. Dietrans-Form ist stabiler als diecis-Form, die Zersetzung wird durch Al₂O₃ nicht beeinflu\t. [PtAox ₃Cl]Cl wird infolge der Erhitzung in die stabileretrans-Form [PtAox ₂Cl₂] umgewandelt und verhält sich auch weiterhin wie diese.

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A contribution to the study of the compounds of Pt(II) with acetoxime

The thermal decomposition ofcis- andtrans-[PtAox ₂Cl₂] and of [PtAox ₃Cl]Cl was studied by means ofTGA andTDA on pure substances as well as on mixtures with Al₂O₃ (1:3). Thetrans form is more stable then thecis form, the presence of Al₂O₃ has no influence on its decomposition. The [PtAox ₃Cl]Cl is transformed by heating into the more stabletrans-isomer and its further behaviour is identical with that of thetrans isomer.

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Mit 4 Abbildung     

Study of occupational health impact of atmospheric pollution on exposed workers at an iron and steel complex by using neutron activation analysis of scalp hair

The occupational health impact of atmospheric pollution on exposed workers at one iron and steel complex was studied by instrumental neutron activation analysis of workers' hair samples and medical examination. The experimental results indicate that there is a positive correlation between the high inhalation amounts of iron and other trace elements by the exposed workers and the symptom of their high blood pressure and hypoglycemia, which implies that the atmospheric environment polluted by iron and steel industry has an adverse health impact on the exposed workers. The measures to relieve and abate the occupational diseases caused by air-borne particulate matter should be taken     

Determination of Mg,Al, P,Cu and Mn in biological fluids by neutron activation analysis

Thermal and epithermal neutron activation analysis has been applied to determine the concentrations of magnesium, aluminium, phosphorus, copper and manganese in two biological fluids: blood serum and market milk. Both epithermal neutron irradiation and radiochemical separation (a chromatographic column of HAP) were used to get rid of the interferences from 24-Na. Strongly acidic solutions of the irradiated samples were passed through the columns of HAP, where sodium was completely adsorbed while, Al, Cu, Mg and Mn were eluted with an efficiency of 99±1%. Since both Al and P were determined through the formation of²⁸Al (2.24 min) thermal and epithermal neutron activation have been applied in order to determine the contribution of each radionuclide to²⁸Al activity. The determination of Mg, Al and P in milk samples was done instrumentally, whereas in the case of blood serum with higher concentration of Na, a radiochemical separation is essential in both cases. The concentrations of Al, Cu, Mg, Mn and P in blood serum and market milk were found to be 0.24±0.02 and 1.85±0.09 g Al/ml, 1.35±0.04 and 0.068±0.005 g Cu/ml, 22.9±1 and 98.9±8.6 g Mg/ml, 22±3 and 16±2 ng Mn/ml and 167±13 and 865±32 g P/ml, respectively.     

Reactions of dithiocarbamic acids derived from alkaloids, morpholine, and piperidine with acrylic acid and its derivatices

-(Thiocarbamoylthio)propionic acids derived from alkaloids, morpholine, and piperidine and their esters, amides, and nitriles were prepared by reactions of the corresponding dithiocarbamic acids with acrylic acid and its derivatives. Some of the compounds were tested for insecticidal activity.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1336–1339.Original Russian Text Copyright © 2004 by Zhivotova, Gazaliev, Ibraev, Fazylov, Kasenov.     

Reaktionen mit Blei(IV)-acetat,XVI. Eine neuartige Umwandlung von 2-Acetoxy-3-oxo-4,5-epoxy-steroiden

Treatment of 3-oxo-4, 5-oxido steroids with lead tetraacetate results in acetoxylation in the 2α-position as could be shown by independent synthesis of the acetoxylated compounds. The products of this reaction rearrange even under very mild conditions (chromatography on silicagel or alumina) to the corresponding 2,3-dioxo-Δ⁴ compounds. The influence of structure and conformation of the various intermediates on their NMR.-spectra is discussed. A mechanism for this new transformation is proposed.     

Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

A short synthesis of the erythrina skeleton and of (+/-)-alpha-lycorane

[reaction: see text] A new nonchain 5-endo radical cyclization starting with xanthates was exploited in a short synthesis of (+/-)-alpha-lycorane and the erythrina ring system.